Solar control multilayer film

ABSTRACT

A multilayer film article is disclosed. The multilayer film article includes an infrared light reflecting multilayer film having alternating layers of a first polymer type and a second polymer type, a hardcoat layer that is the reaction product of a mixture that includes a curable, crosslinkable fluoro-acrylate-containing compound; a curable, crosslinkable non-fluorinated organic compound; infrared light absorbing nanoparticles; and a polymerization initiator. The hardcoat layer being disposed adjacent the multilayer film.

BACKGROUND

The present invention generally relates to solar control multilayerfilm. The present invention more particularly relates to solar controlmultilayer film that includes infrared absorbing nanoparticles andfluoromaterials that impart desirable properties.

Dyed and vacuum-coated plastic films have been applied to windows toreduce heat load due to sunlight. To reduce heat load, solartransmission is blocked in either the visible or the infrared portionsof the solar spectrum, i.e., at wavelengths ranging from 400 nm to 2500nm or greater.

Primarily through absorption, dyed films can control the transmission ofvisible light and consequently provides glare reduction. However, dyedfilms generally do not block near-infrared solar energy and consequentlyare not completely effective as solar control films. Dyed films alsooften fade with solar exposure. In addition, when films are colored withmultiple dyes, the dyes often fade at different rates, causing anunwanted color changes over the life of the film.

Other known window films are fabricated using vacuum-deposited greymetals, such as stainless steel, inconel, monel, chrome, or nichromealloys. The deposited grey metal films offer about the same degrees oftransmission in the visible and infrared portions of the solar spectrum.As a result, the grey metal films are an improvement over dyed filmswith regard to solar control. The grey metal films are relatively stablewhen exposed to light, oxygen, and/or moisture, and in those cases inwhich the transmission of the coatings increases due to oxidation, colorchanges are generally not detectable. After application to clear glass,grey metals block light transmission by approximately equal amounts ofsolar reflection and absorption.

Vacuum-deposited layers such as silver, aluminum, and copper controlsolar radiation primarily by reflection and are useful only in a limitednumber of applications due to the high level of visible reflectance. Amodest degree of selectivity (i.e., higher visible transmission thaninfrared transmission) is afforded by certain reflective materials, suchas copper and silver.

There is a need for improved solar control film that has a high visiblelight transmission and substantially blocks infrared radiation, and hasdesirable cleaning and scratch resistant properties.

SUMMARY

Generally, the present invention relates to solar control multilayerfilm. The present invention more particularly relates to solar controlmultilayer film that includes infrared absorbing nanoparticles andfluoromaterials that impart desirable properties.

The invention includes articles having an infrared light reflectingmultilayer film having alternating layers of a first polymer type and asecond polymer type; and a hardcoat layer disposed on the multilayerfilm, wherein the hardcoat layer includes infrared light absorbingnanoparticles dispersed therein and wherein the hardcoat layer has astatic contact angle of water that is greater than 70 degrees, and astatic contact angle of hexadecane that is greater than 50 degrees.

The invention also includes articles having an infrared light reflectingmultilayer film having alternating layers of a first polymer type and asecond polymer type; and a hardcoat layer disposed on the multilayerfilm, wherein the hardcoat layer is the reaction product of a mixturethat includes at least one curable, crosslinkablefluoro-acrylate-containing compound; at least one curable, crosslinkablenon-fluorinated compound; infrared light absorbing nanoparticles; and atleast one polymerization initiator.

Exemplary fluoro-acrylate-containing compounds include:

R_(f)QXC(O)NH))_(m)—R_(i)—(NHC(O)OQ(A)_(a))_(n)   (Formula 1)

wherein R_(i) is a residue of a multi-isocyanate. Representative R_(i)includes, but is not limited to,

X is O, S or NR, where R is H or lower alkyl of 1 to 4 carbon atoms;

R_(f) is a monovalent perfluoropolyether moiety composed of groupscomprising the formula F(R_(fc)O)_(x)C_(d)F_(2d)—, wherein each R_(fc)independently represents a fluorinated alkylene group having from 1 to 6carbon atoms. Exemplary monovalent perfluoropolyethers of R_(fc)Oinclude, but are not limited to, those that have perfluorinatedrepeating units of —(C_(p)F_(2p))—, —(C_(p)F_(2p)O)—, —(CF(Z))-,—(CF(Z)O)—, —(CF(Z)C_(p)F_(2p)O)—, —(C_(p)F_(2p)CF(Z)O)—, —(CF₂CF(Z)O)—,or combinations thereof. In these repeating units, p is typically aninteger of 1 to 10. In some embodiments, p is an integer of 1 to 8, 1 to6, 1 to 4, or 1 to 3. The group Z is F, a perfluoroalkyl group,perfluoroether group, perfluoropolyether, or a perfluoroalkoxy group,all of which can be linear, branched, or cyclic. The Z group typicallyhas no more than 12 carbon atoms, no more than 10 carbon atoms, no morethan 9 carbon atoms, no more than 4 carbon atoms, no more than 3 carbonatoms, no more than 2 carbon atoms, or no more than 1 carbon atom. Insome embodiments, the Z group can have no more than 4 oxygen atoms, nomore than 3 oxygen atoms, no more than 2 oxygen atoms, no more than 1oxygen atoms, or no oxygen atoms. In these perfluoropolyetherstructures, the different repeating units can be distributed randomlyalong the chain. C_(d)F_(2d) can be linear or branched. Each xindependently represents an integer greater than or equal to 2, andwherein d is an integer from 1 to 8; The number average molecular weightof R_(f) can be from 400 to 5000, in another embodiment from 800 to4000, and in yet another embodiment from 1000 to 3000.

Q is independently a connecting group of valency at least 2, including,but not limited to —C(O)NR(CH₂)_(h)—, —C(O)NRCH₂CH(CH₂—)CH₂—,—C(O)NRCH₂CH(CH₂—)₂, —(CH₂)_(h)—, —SO₂NR(CH₂)_(h)—,—(CH₂)_(h)—O—(CH₂)_(j)—, —(CH₂)_(h)—S—(CH₂)_(j)—, —CH₂C[(CH₂—)]₃ whereinR is H or lower alkyl of 1 to 4 carbon atoms, h is from 1 to 30, and jis from 2 to 20;

A is a (meth)acryl functional group —XC(O)C(R²)═CH₂, wherein R² is alower alkyl of 1 to 4 carbon atoms or H or F;

m is at least 1;

n is at least 1;

a is 1 to 6, with the proviso that m+n is 2 to 10, and in which eachunit referred to by the subscripts m and n is attached to an R_(i) unit.

Specific examples of compounds that fit within Formula (1) are shownbelow

Other exemplary fluoro-acrylate-containing compounds include:

R_(f2)-[Q-(XC(O)NHQOC(O)C(R²)═CH₂)_(a)]_(g)   (Formula 5)

wherein X,Q, R² and a are as defined above; and

g is 1 or 2;

R_(f2) is either a monovalent perfluoropolyether moiety composed ofgroups comprising the formula F(R_(fc)O)_(x)C_(d)F_(2d)— or a divalentperfluoropolyether moiety composed of groups comprising the formula—C_(d)F_(2d)O(R_(fc)O)_(x)C_(d)F_(2d)—, in which R_(fc), x, and d are asdefined above. The number average molecular weight of R_(f) can be from400 to 5000, 800 to 4000, and 1000 to 3000.

Examples of specific fluoro-acrylate-containing compounds that can beutilized in hardcoat compositions of the invention include, but are notlimited to, HFPO—C(O)NHC₂H₄OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂,HFPO—[C(O)NHC₂H₄OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂]₂,HFPO—C(O)NHCH₂CH[OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂]CH₂OC(O)NHC₂H₄OC(O)C(CH₃)═CH,HFPO—C(O)NHC(C₂H₅)(CH₂OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂)₂,CH₂═C(CH₃)C(O)OC₂H₄NHC(O)OC₂H₄NHC(O)—HFPO—C(O)NHC₂H₄OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂,or combinations thereof.

Still other exemplary fluoro-acrylate-containing compounds include:

wherein R_(i), X, R_(f), Q, a, m ,n, and A are as identified before; and

G is alkyl, aryl, alkaryl, aralkyl group, substituted alkyl/aryl groupwith functional group or a combination thereof. Representative examplesof functional groups include, but are not limited to, —Si(OMe)₃,—(C₂H₄O)_(i)R³, and —CO₂R³; wherein R³ is a alkyl of 1 to 30 carbonatoms, and i is from 5 to 5000;

o is at least 1;

Still other exemplary fluoro-acrylate-containing compounds include:

wherein R_(f), Q, X, A, R_(i), m, a, and n are as defined above; and

D is a divalent or q-valent isocyanate reactive group containingresidue, D(XH)_(q), examples of which include alkylene, arylene,alkarylene, fluoroalkylene, perfluoroalkylene, or aralkylene, which canbe linear, brianched or cyclic, optionally include heteroatoms such asO, N, and S. q is from 2 to 6. In one embodiment q is 2.

Formula 4 is the reaction product from R_(i)(NCO)_(m+n+1) and D(XH)₂,such as a diol, dithiol or diamine to form(OCN)_(m+n)R_(i)—NHC(O)X-D-XC(O)NH—R_(i)(NCO)_(m+n), followed by thereaction with R_(f)-Q-XH and (A)_(a)-Q-OH. Multi-isocyanate reactivechemical, D(XH)_(q), could also have been used to obtain compoundssimilar to Formula 4 by replacing D(XH)₂. Representative diols ofD(QXH)_(q), where q is 2, include, but are not limited to,non-fluorinated diol such as HO(CH₂)₂OH, HO(CH₂)₄OH, HO(CH₂)₆OH,HO(CH₂)₁₀OH and HO(CH₂)₂O(CH₂)₂OH; fluorochemical diols such asHOCH₂(CF₂)₄CH₂OH, C₄F₉SO₂N(CH₂CH₂OH)₂, HFPO—C(O)NHCH₂CH₂CH₂N(CH₂CH₂OH)₂,HOCH₂CH₂NHC(O)—HFPO—C(O)NHCH₂CH₂OH,HOCH₂CH₂NHC(O)—CF₂(OCF₂)_(x1)(CF₂CF₂O)_(x2)CF₂—C(O)NHCH₂CH₂OH,HOCH₂—CF₂(OCF₂)_(x1)(CF₂CF₂O)_(x2)CF₂—CH₂OH, andH(OCH₂C(CH₃)(CH₂OCH₂CF₃)CH₂)_(x)OH (Fox-Diol, having a MW about 1342 andavailable from Omnova Solutions Inc. of Akron, Ohio); and functionalizeddiol such as CH₃N(CH₂CH₂OH)₂, hydantoin hexaacrylate (HHA), prepared asdescribed in Example 1 of U.S. Pat. No. 4,262,072 to Wendling et al, andCH₂═C(CH₃)C(O)OCH₂CH(OH)CH₂O(CH₂)₄OCH₂CH(OH)CH₂OC(O)C(CH₃)═CH₂.

When D contains —C_(d)F_(2d)O(R_(fc)O)_(x)C_(d)F_(2d)—, m is optionallyzero.

Yet other exemplary fluoro-acrylate-containing compounds includefluoro-acrylate-non-urethane compounds of Formula 5:

(R_(f2))-[(Q)-(R_(A))_(a)]_(g)   (Formula 5)

wherein R_(f2) is a monovalent perfluoropolyether moiety composed ofgroups comprising the formula F(R_(fc)O)_(x)C_(d)F_(2d)—, or divalentperfluoropolyether group composed of groups comprising the formula—C_(d)F_(2d)O(R_(fc)O)_(x)C_(d)F_(2d)— with number average molecularweight 400 to 5000, in one embodiment 800 to 4000, in another embodiment1000 to 3000, wherein R_(fc), d, and x are as defined above;

Q is as identified before; and

R_(A) is a is a free-radically reactive such as (meth)acryl, allyl, orvinyl, group; a is 1 to 6, and g is 1 or 2.

Exemplary fluoro-acrylate-non-urethane compounds with (meth)acryl groupof Formula 5 that can be utilized in hardcoat compositions of theinvention include, but are not limited to, HFPO—C(O)NHCH₂CH₂OC(O)CH═CH₂,HFPO—C(O)NHCH₂CH₂OC(O)C(CH₃)═CH₂,HFPO—[C(O)NHCH₂CH₂OC(O)CH═CH₂]₂,HFPO—C(O)NHCH₂CH═CH₂, HFPO—[C(O)NHCH₂CH═CH₂]₂, HFPO—C(O)NHCH₂CH₂OCH₂CH₂OC(O)CH═CH₂, HFPO—[C(O)NHCH₂CH₂OCH₂CH₂OCH₂CH₂OC(O)CH═CH₂]₂,HFPO—C(O)NH—(CH₂)₆OC(O)CH═CH₂, HFPO—C(O)NHC(CH₂OC(O)CH═CH₂)₃,HFPO—C(O)N(CH₂CH₂OC(O)CH═CH₂)₂, HFPO—C(O)NHCH₂CH₂N(C(O)CH═CH₂)CH₂OC(O)CH═CH₂, HFPO—C(O)NHC(CH₂OC(O)CH═CH₂)₂H,HFPO—C(O)NHC(CH₂OC(O)CH═CH₂)₂CH₃, HFPO—C(O)NHC(CH₂OC(O)CH═CH₂)₂CH₂CH₃,HFPO—C(O)NHCH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂,HFPO—[C(O)NHCH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂]₂,HFPO—C(O)NHCH₂CH₂CH₂N(CH₂CH₂OC(O)CH═CH₂)₂,HFPO—C(O)OCH₂C(CH₂OC(O)CH═CH₂)₃,CH₂═CHC(O)OCH₂CH(OC(O)—HFPO)CH₂OCH₂CH(OH)CH₂OCH₂CH(OC(O)—HFPO)CH₂OCOCH═CH₂,HFPO—CH₂OCH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂, HFPO—CH₂OC(O)CH═CH₂,HFPO—CH₂CH₂OC(O)CH═CH₂, HFPO—CH₂CH₂OC(O)C(CH₃)═CH₂,HFPO—CH₂CH₂OCH₂CH₂OC(O)CH═CH₂, or combinations thereof.

Still other exemplary fluoro-acrylate-containing compounds include:

R_(f3)-J-OC(O)NH—K—HNC(O)—(C_(b)H_(2b))CH_((3-v))((C_(y)H_(2y))OC(O)C(R²)═CH₂)_(v)  (Formula 6)

wherein, R_(f3) is a monovalent perfluoroalkyl group or apolyfluoroalkyl group which can be linear, branched, or cyclic.Exemplary R_(f3) includes, but is not limited to, C_(d)F_(2d+1—,)

wherein d is 1 to 8; CF₃CF₂CF₂CHFCF₂—; CF₃CHFO(CF₂)₃—; (CF₃)₂NCF₂CF₂—;CF₃CF₂CF₂OCF₂CF₂—; CF₃CF₂CF₂OCHCF₂—; n-C₃F₇OCF(CF₃)—; H(CF₂CF₂)₃—; orn-C₃F₇OCF(CF₃)CF₂OCF₂—.

J is a divalent linkage group, selected from, but not limited to,

R is H or an alkyl group of 1 to 4 carbon atoms;

h is 1 to 30;

j is 2 to 10;

K is the residue of a diisocyanate with an unbranched symmetric alkylenegroup, arylene group, or aralkylene group; Exemplary K includes, but isnot limited to, —(CH₂)₆—,

b is 1 to 30;

v is 1 to 3;

y is 1 to 6; and

R² is H, CH_(3,) or F.

Exemplary fluoro-acrylate-compounds with (meth)acryl group of Formula 6that can be utilized in hardcoat compositions of the invention include,but are not limited to,C₄F₉SO₂N(CH₃)C₂H₄O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(MeFBSE-MDI-HEA),C₄F₉SO₂N(CH₃)C₂H₄O—C(O)NH(CH₂)₆NHC(O)—OC₂H₄OC(O)Me=CH₂(MeFBSE-HDI-HEMA),C₄F₉SO₂N(CH₃)C₂H₄O—C(O)NH(CH₂)₆NHC(O)—OC₄H₈OC(O)CH═CH₂ (MeFBSE-HDI-BA),C₄F₉SO₂N(CH₃)C₂H₄O—C(O)NH(CH₂)₆NHC(O)—OC₁₂H₂₄OC(O)CH═CH₂(MeFBSE-HDI-DDA), CF₃CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(CF₃CH₂OH-MDI-HEA),C₄F₉CH₂CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₄F₉CH₂CH₂OH-MDI-HEA),C₆F₁₃CH₂CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₆F₁₃CH₂CH₂OH-MDI-HEA),C₃F₇CHFCF₂CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₃F₇CHFCF₂CH₂OH-MDI-HEA),CF₃CHFO(CF₂)₃CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(CF₃CHFO(CF₂)₃CH₂O-MDI-HEA),C₃F₇OCHFCF₂CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₃F₇OCHFCF₂CH₂OH-MDI-HEA),C₃F₇OCF(CF₃)CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₃F₇OCF(CF₃)CH₂OH-MDI-HEA),C₄F₉SO₂NMeC₂H₄O—C(O)NHC₆H₄CH₂C₆H₄NHC(O)—OCH₂C(CH₂OC(O)CH═CH₂)₃(MeFBSE-MDI-(SR-444C)),or combinations thereof.

The invention also includes light control articles for blocking infraredlight from an infrared light source that include an infrared lightreflecting multilayer film having alternating layers of a first polymertype and a second polymer type; a hardcoat layer disposed on themultilayer film, wherein the hardcoat layer is the reaction product of amixture that includes: a curable, crosslinkablefluoro-acrylate-containing compound; a curable, crosslinkablenon-fluorinated organic compound; infrared light absorbingnanoparticles; and a polymerization initiator; and a substrate disposedadjacent the infrared light reflecting multilayer film.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application may be more completely understood inconsideration of the following detailed description of variousembodiments of the invention in connection with the accompanyingdrawings, in which:

FIG. 1 is a perspective view of a multilayer film;

FIG. 2 schematically illustrates an embodiment of a solar controlmultilayer film article; and

FIG. 3 schematically illustrates another embodiment of a solar controlmultilayer film article.

While the invention is amenable to various modifications and alternativeforms, specifics thereof have been shown by way of example in thedrawings and will be described in detail. It should be understood,however, that the intention is not to limit the invention to theparticular embodiments described. On the contrary, the intention is tocover all modifications, equivalents, and alternatives falling withinthe spirit and scope of the invention.

DETAILED DESCRIPTION

The solar control multilayer film of the present invention is believedto be applicable to a variety of applications needing solar controlincluding, for example, architectural and transportation applications.In some embodiments, the solar control multilayer film article includesan infrared absorbing nanoparticle layer disposed on an infraredreflecting multilayer film. In other embodiments, the solar controlmultilayer film article includes an infrared reflecting multilayer filmdisposed between an infrared absorbing nanoparticle layer and anadhesive layer. The solar control film can be adhered to an opticalsubstrate such as, for example, a glass substrate. These examples, andthe examples discussed below, provide an appreciation of theapplicability of the disclosed solar control multilayer film, but shouldnot be interpreted in a limiting sense.

The term “polymer” or “polymeric” will be understood to includepolymers, copolymers (e.g., polymers formed using two or more differentmonomers), oligomers and combinations thereof, as well as polymers,oligomers, or copolymers. Both block and random copolymers are included,unless indicated otherwise.

As used herein, “fluoro-acrylate-containing compound” or“fluoro-acrylate-containing additive”; or “fluoro-acrylate-non-urethanecompound” or “fluoro-acrylate-non-urethane additive” can refer to aspecific compound or a mixture of compounds.

Unless otherwise indicated, all numbers expressing feature sizes,amounts, and physical properties used in the specification and claimsare to be understood as being modified in all instances by the term“about.”0 Accordingly, unless indicated to the contrary, the numericalparameters set forth in the foregoing specification and attached claimsare approximations that can vary depending upon the desired propertiessought to be obtained by those skilled in the art utilizing theteachings disclosed herein.

The term “hard resin” or “hardcoat” means that the resulting curedpolymer exhibits an elongation at break of less than 50 or 40 or 30 or20 or 10 or 5 percent when evaluated according to the ASTM D-882-91procedure. In some embodiments, the hard resin polymer can exhibit atensile modulus of greater than 100 kpsi (6.89×10⁸ pascals) whenevaluated according to the ASTM D-882-91 procedure. In some embodiments,the hard resin polymer can exhibit a haze value of less than 10% or lessthan 5% when tested in a Taber abrader according to ASTM D 1044-99 undera load of 500 g and 50 cycles (haze can be measured with Haze-Gard Plus,BYK-Gardner, MD, haze meter).

As used in the context of the hardcoat composition, a “weight percent”or “wt-% ” of a particular component refers to the amount (by weight) ofthe particular component in the hardcoat composition after the solventhas been removed from the hardcoat composition but before the hardcoatcomposition has been cured to form the hardcoat layer.

The term “adjacent” refers to one element being in close proximity toanother element and includes the elements touching one another andfurther includes the elements being separated by one or more layersdisposed between the elements.

The recitation of numerical ranges by endpoints includes all numberssubsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3,3.80, 4, and 5) and any range within that range.

As used in this specification and the appended claims, the singularforms “a”, “an”, and “the” include plural referents unless the contentclearly dictates otherwise. Thus, for example, reference to acomposition containing “a nanoparticle layer” includes two or morenanoparticle layers. As used in this specification and the appendedclaims, the term “or” is generally employed in its sense including“and/or” unless the content clearly dictates otherwise.

This disclosure generally describes multilayer film that includes aninfrared absorbing nanoparticle layer disposed on polymeric multilayerfilm. In many embodiments, an infrared light reflecting multilayer filmhas alternating layers of a first polymer type and a second polymertype, and an infrared light absorbing nanoparticle layer is adjacent themultilayer film. The nanoparticle layer includes a plurality of metaloxide nanoparticles. In some embodiments, the multilayer film isdisposed adjacent to an optical substrate such as glass to form a solarcontrol article. In some embodiments, the multilayer film has an averagevisible light transmission of at least 45% and an average infraredtransmission for 780 nm to 2500 nm light of less than 15%.

FIG. 1 illustrates multilayer optical film 20. The film includesindividual layers 22, 24. The layers have different refractive indexcharacteristics so that some light is reflected at interfaces betweenadjacent layers. The layers are sufficiently thin so that lightreflected at a plurality of the interfaces undergoes constructive ordestructive interference in order to give the film the desiredreflective or transmissive properties. For optical films designed toreflect light at ultraviolet, visible, or near-infrared wavelengths,each layer generally has an optical thickness (i.e., a physicalthickness multiplied by refractive index) of less than about 1micrometer. Thicker layers can, however, also be included, such as skinlayers at the outer surfaces of the film, or protective boundary layersdisposed within the film that separate packets of layers.

The reflective and transmissive properties of multilayer optical film 20are a function of the refractive indices of the respective layers (i.e.,microlayers). Each layer can be characterized at least in localizedpositions in the film by in-plane refractive indices n_(x), n_(y), and arefractive index n_(z) associated with a thickness axis of the film.These indices represent the refractive index of the subject material forlight polarized along mutually orthogonal x-, y- and z-axes,respectively (see FIG. 1). In practice, the refractive indices arecontrolled by judicious materials selection and processing conditions.Film 20 can be made by co-extrusion of typically tens or hundreds oflayers of two alternating polymers A, B, followed by optionally passingthe multilayer extrudate through one or more multiplication dies, andthen stretching or otherwise orienting the extrudate to form a finalfilm. The resulting film is composed of typically tens or hundreds ofindividual layers whose thicknesses and refractive indices are tailoredto provide one or more reflection bands in desired region(s) of thespectrum, such as in the visible, near infrared, and/or infrared. Inorder to achieve high reflectivity with a reasonable number of layers,adjacent layers can exhibit a difference in refractive index (Δn_(x))for light polarized along the x-axis of at least 0.05. In someembodiments, if the high reflectivity is desired for two orthogonalpolarizations, then the adjacent layers also exhibit a difference inrefractive index (Δn_(y)) for light polarized along the y-axis of atleast 0.05. In other embodiments, the refractive index difference Δn_(y)can be less than 0.05 or 0 to produce a multilayer stack that reflectsnormally incident light of one polarization state and transmits normallyincident light of an orthogonal polarization state.

If desired, the refractive index difference (Δn_(z)) between adjacentlayers for light polarized along the z-axis can also be tailored toachieve desirable reflectivity properties for the p-polarizationcomponent of obliquely incident light. For ease of explanation, at anypoint of interest on a multilayer optical film the x-axis will beconsidered to be oriented within the plane of the film such that themagnitude of Δn_(x) is a maximum. Hence, the magnitude of Δn_(y) can beequal to or less than (but not greater than) the magnitude of Δn_(x).Furthermore, the selection of which material layer to begin with incalculating the differences Δn_(x), Δn_(y), Δn_(z), is dictated byrequiring that Δn_(x) be non-negative. In other words, the refractiveindex differences between two layers forming an interface areΔn_(j)=n_(1j)−n_(2j), where j=x, y, or z and where the layerdesignations 1, 2 are chosen so that n_(1x)≧n_(2x)., i.e., Δn_(x)≧0.

To maintain high reflectivity of p-polarized light at oblique angles ofincidence, the z-index mismatch Δn_(z) between layers can be controlledto be substantially less than the maximum in-plane refractive indexdifference Δn_(x), such that Δn_(z)≦0.5*Δn_(x). In one embodiment,Δn_(z)≦0.25*Δn_(x). A zero or near zero magnitude z-index mismatchyields interfaces between layers whose reflectivity for p-polarizedlight is constant or near constant as a function of incidence angle.Furthermore, the z-index mismatch Δn_(z) can be controlled to have theopposite polarity compared to the in-plane index difference Δn_(x), i.e.Δn_(z)<0. This condition yields interfaces whose reflectivity forp-polarized light increases with increasing angles of incidence, as isthe case for s-polarized light.

Multilayer optical films have been described in, for example, U.S. Pat.No. 3,610,724 (Rogers); U.S. Pat. No. 3,711,176 (Alfrey, Jr. et al.),“Highly Reflective Thermoplastic Optical Bodies For Infrared, Visible orUltraviolet Light”; U.S. Pat. No. 4,446,305 (Rogers et al.); U.S. Pat.No. 4,540,623 (Im et al.); U.S. Pat. No. 5,448,404 (Schrenk et al.);U.S. Pat. No. 5,882,774 (Jonza et al.) “Optical Film”; U.S. Pat. No.6,045,894 (Jonza et al.) “Clear to Colored Security Film”; U.S. Pat. No.6,531,230 (Weber et al.) “Color Shifting Film”; PCT Publication WO99/39224 (Ouderkirk et al.) “Infrared Interference Filter”; and USPatent Publication 2001/0022982 A1 (Neavin et al.), “Apparatus ForMaking Multilayer Optical Films”, all of which are incorporated hereinby reference. In such polymeric multilayer optical films, polymermaterials are used predominantly or exclusively in the makeup of theindividual layers. Such films can be compatible with high volumemanufacturing processes, and may be made in large sheets and roll goods.

The multilayer film can be formed by any useful combination ofalternating polymer type layers. In many embodiments, at least one ofthe alternating polymer layers is birefringent and oriented. In someembodiments, one of the alternating polymer layer is birefringent andorientated and the other alternating polymer layer is isotropic. In oneembodiment, the multilayer optical film is formed by alternating layersof a first polymer type including polyethylene terephthalate (PET) orcopolymer of polyethylene terephthalate (coPET) and a second polymertype including poly(methyl methacrylate) (PMMA) or a copolymer ofpoly(methyl methacrylate) (coPMMA). In another embodiment, themultilayer optical film is formed by alternating layers of a firstpolymer type including polyethylene terephthalate and a second polymertype including a copolymer of poly(methyl methacrylate and ethylacrylate). In another embodiment, the multilayer optical film is formedby alternating layers of a first polymer type including a glycolatedpolyethylene terephthalate (PETG—a copolymer ethylene terephthalate anda second glycol moiety such as, for example, cyclohexanedimethanol) or acopolymer of a glycolated polyethylene terephthalate (coPETG) and secondpolymer type including polyethylene naphthalate (PEN) or a copolymer ofpolyethylene naphthalate (coPEN). In another embodiment, the multilayeroptical film is formed by alternating layers of a first polymer typeincluding polyethylene naphthalate or a copolymer of polyethylenenaphthalate and a second polymer type including poly(methylmethacrylate) or a copolymer of poly(methyl methacrylate). Usefulcombination of alternating polymer type layers are disclosed in U.S.Pat. No. 6,352,761 and U.S. Pat. No. 6,797,396, which are incorporatedby reference herein.

FIG. 2 schematically illustrates an embodiment of a solar controlmultilayer film article 100. The film 100 includes an infrared lightreflecting multilayer film 110 having alternating layers of a firstpolymer type and a second polymer type, as described above. An infraredlight absorbing hardcoat layer 120 is disposed adjacent the multilayerfilm 110. An adhesive layer 130 is disposed on the multilayer film 110.A release layer or substrate 140 is disposed on the adhesive layer 130.An optional second hardcoat layer 150 can be disposed adjacent themultilayer film 110.

In many embodiments, the film 100 includes an infrared light reflectingmultilayer film 110 having alternating layers of a first polymer typeand a second polymer type, as described above and a hardcoat layer 120is disposed adjacent the multilayer film 110. In some embodiments, thehardcoat layer 120 includes a metal oxide dispersed within a curedpolymeric binder. In some embodiments, this hardcoat layer 120 has athickness in a range from 1 to 20 micrometers, or from 1 to 10micrometers, or from 1 to 5 micrometers. An adhesive layer 130 isdisposed on the multilayer film 110. A release layer or opticalsubstrate 140 is disposed on the adhesive layer 130.

FIG. 3 schematically illustrates another embodiment of a solar controlmultilayer film article 200. The film 200 includes an infrared lightreflecting multilayer film 210 having alternating layers of a firstpolymer type and a second polymer type, as described above. A hardcoatlayer 220 is disposed adjacent the multilayer film 210. An optionalintermediate adhesive layer 270 is disposed between the hardcoat layer220 and the multilayer film 210. An adhesive layer 230 is disposed onthe multilayer film 210. A release layer or optical substrate 240 can bedisposed on the pressure sensitive adhesive layer 230. An optionalsecond hardcoat layer 250 can be disposed adjacent the multilayer film210. An optional intermediate polymeric layer 260 is disposed betweenthe optional second hardcoat layer 250 and the intermediate adhesivelayer 270.

The above multilayer film article constructions provide improved solarcontrol film articles. In some embodiments, the multilayer film articlehas an average visible light transmission (400 to 780 nm) of at least45% and an average infrared light transmission for 780 nm to 2500 nmlight of less than 10% or less than 15%. In some embodiments, themultilayer film article has an average visible light transmission of atleast 60% and an infrared light transmission of 20% or less forsubstantially all wavelengths between 950 nm and 2500 nm. In someembodiments, the multilayer film article has an average light reflectionbetween 780 and 1200 nm of 50% or greater and an average lighttransmission between 1400 and 2500 nm of 50% or less. In furtherembodiments, the multilayer film article has an average light reflectionbetween 780 and 1200 nm of 80% or greater and an average lighttransmission between 1400 and 2500 nm of 20% or less. In still furtherembodiments, the multilayer film article has an average light reflectionbetween 780 and 1200 nm of 90% or greater and an average lighttransmission between 1400 and 2500 nm of 5% or less.

In one embodiment of the invention, the hardcoat layer that is formedfrom a hardcoat mixture includes infrared light absorbing materials, andthe hardcoat layer has a static contact angle of water that is greaterthan 70 degrees. In yet another embodiment, the hardcoat layer has astatic contact angle of water that is greater than 90 degrees. In afurther embodiment, the hardcoat layer has a static contact angle ofwater that is greater than 100 degrees.

In one embodiment of the invention, the hardcoat layer has a staticcontact angle of hexadecane (oil) that is greater than 50 degrees.

In one embodiment of the invention, a combination of low surface energy(e.g. anti-soiling, stain resistant, oil and/or water repellency) anddurability (e.g. abrasion resistance) are desirable properties for thehardcoat layer. The hardcoat layer can also function, in someembodiments of the invention, to decrease glare loss while improvingdurability and optical clarity.

The surface energy can be characterized by various methods such ascontact angle and ink repellency, as determined by the test methodsdescribed in the Examples. In this application, “stain repellent” refersto a surface treatment exhibiting a static contact angle with water ofat least 70 degrees. In one embodiment, the contact angle is at least 80degrees and in another embodiment at least 90 degrees. Alternatively, orin addition thereto, the advancing contact angle with hexadecane is atleast 50 degrees and in another embodiment at least 60 degrees. Lowsurface energy results in anti-soiling and stain repellent properties aswell as rendering the exposed surface easy to clean. Another indicatorof low surface energy relates to the extent to which ink from a pen ormarker beads up when applied to the exposed surface. The surface layerand articles exhibit “ink repellency” when ink from pens and markersbeads up into discrete droplets and can be easily removed by wiping theexposed surface with tissues or paper towels, such as tissues availablefrom the Kimberly Clark Corporation, Roswell, Ga. under the tradedesignation “SURPASS FACIAL TISSUE.”

Durability can be defined in terms of results from the combination ofsolvent resistance tests and abrasion resistance tests with Steel Woolobtained from Rhodes-American, a division of Homax Products, Bellingham,Wash. under the trade designation “#0000-Super-Fine”, with 500 gramsweight applied to the stylus and scratched for 300 times, as describedin Examples.

In some embodiments, the metal oxide nanoparticles include indium tinoxide, doped indium tin oxide, antimony tin oxide, or doped antimony tinoxide dispersed in a polymeric material. The nanoparticle layer can haveany useful thickness such as, for example, from 1 to 10 or 2 to 8micrometers. The nanoparticle layer can include nanoparticles at anyuseful loading or wt % such as, for example, 30 to 90 wt %, 40 to 80 wt%, or 50 to 80 wt %. In many embodiments, the nanoparticle layer isnonconducting. Nanoparticle compositions are commercially availablefrom, for example, Advanced Nano Products Co., LTD., South Korea, underthe tradenames TRB-PASTE™ SM6080(B), SH7080, SL6060. In anotherembodiment, the metal oxide nanoparticles include zinc oxide and/oraluminum oxide, such oxides are available from GfE Metalle undMaterialien GmbH, Germany.

The adhesive layer 130 described above can include any type of adhesivethat enables the solar control multilayer film to be affixed to thesubstrate. In order to attach the solar control film to the glass, onesurface of the solar control film is coated with the adhesive and arelease sheet is removed from the adhesive layer before application ofthe film to the substrate. Ultra-violet absorption additives can beincorporated into the adhesive layer.

In one embodiment, the adhesive of the adhesive layer 130 is a pressuresensitive adhesive (PSA). In another embodiment, the adhesive is amoisture curable adhesive. In embodiments utilizing a PSA, the PSA is anoptically clear PSA film such as a polyacrylate pressure sensitiveadhesive. The Pressure-Sensitive Tape Council has defined pressuresensitive adhesives as material with the following properties: (1)aggressive and permanent tack, (2) adherence with no more than fingerpressure, (3) sufficient ability to hold onto an adherent, (4)sufficient cohesive strength, and (5) requires no activation by anenergy source. PSAs are normally tacky at assembly temperatures, whichis typically room temperature or greater (i.e., about 20° C. to about30° C. or greater). Materials that have been found to function well asPSAs are polymers designed and formulated to exhibit the requisiteviscoelastic properties resulting in a desired balance of tack, peeladhesion, and shear holding power at the assembly temperature. The mostcommonly used polymers for preparing PSAs are natural rubber-, syntheticrubber- (e.g., styrene/butadiene copolymers (SBR) andstyrene/isoprene/styrene (SIS) block copolymers), silicone elastomer-,poly alpha-olefin-, and various (meth) acrylate-(e.g., acrylate andmethacrylate) based polymers. Of these, (meth)acrylate-based polymerPSAs have evolved as one class of PSA for the present invention due totheir optical clarity, permanence of properties over time (agingstability), and versatility of adhesion levels, to name just a few oftheir benefits.

The release liner described above can be formed of any useful materialsuch as, for example, polymers or paper and may include a release coat.Suitable materials for use in release coats include, but are not limitedto, fluoropolymers, acrylics and silicones designed to facilitate therelease of the release liner from the adhesive.

The substrate described above can be formed of any useful material andin many embodiments is an optical substrate. In some embodiments, thesubstrate is formed of a polymeric material such as, for example,cellulose triacetate, polycarbonate, polyacrylate, polypropylene, orpolyethylene terephthalate. In other embodiments, the substrate isformed of an inorganic material such as, for example, quartz, glass,sapphire, YAG, or mica. The substrate can have any useful thickness. Inone embodiment, the substrate is automotive or architectural glass. Insome embodiments including clear glass substrates as a glazing system,the glazing system has a shading coefficient of 0.68 or less, or 0.6 orless, or 0.55 or less, or 0.50 or less, at a T_(VIS) of 70% or greater.

The hardcoat layer can improve the durability of the substrate duringprocessing and during use of the end product. The hardcoat layer caninclude any useful material, such as silica-based hardcoats, siloxanehardcoats, melamine hardcoats, acrylic hardcoats, and the like. Thehardcoat can be any useful thickness such as, for example, from 1 to 20micrometers, or 1 to 10 micrometers, or 1 to 5 micrometers.

In one embodiment of the invention, the hardcoat layer generallyincludes the reaction product of a mixture that includes afluoro-acrylate-containing compound that is curable, and crosslinkable;a curable, crosslinkable non-fluorinated compound; an infrared lightabsorbing material; and a polymerization initiator.

In one embodiment of the present invention, thefluoro-acrylate-containing additive is a perfluoropolyether urethanehaving a monovalent perfluoropolyether moiety and a multi-acrylateterminal group. In such an embodiment, this exemplary additive can becombined with a conventional hydrocarbon-based (for example, anacrylate-based) hard coat material as the curable, crosslinkable,non-fluorinated compound. The additive is added at less than 10 wt-%,and in one embodiment less than 5 wt-%. In yet another embodiment, theadditive is added between 0.05 and 5 wt-%.

Exemplary fluoro-acrylate-containing compounds include:

(R_(f)QXC(O)NH))_(m)—R_(i)—(NHC(O)OQ(A)_(a))_(n)   (Formula 1)

wherein R_(i) is a residue of a multi-isocyanate. Representative R_(i)includes, but is not limited to, such as —(CH₂)₆—,

X is O, S or NR, where R is H or lower alkyl of 1 to 4 carbon atoms;

R_(f) is a monovalent perfluoropolyether moiety composed of groupscomprising the formula F(R_(fc)O)_(x)C_(d)F_(2d)—, wherein each R_(fc)independently represents a fluorinated alkylene group having from 1 to 6carbon atoms. Exemplary monovalent perfluoropolyethers of R_(fc)Oinclude, but are not limited to, those that have perfluorinatedrepeating units of —(C_(p)F_(2p))—, —(C_(p)F_(2p)O)—, —(CF(Z))-,—(CF(Z)O)—, —(CF(Z)C_(p)F_(2p)O)—, —(C_(p)F_(2p)CF(Z)O)—, —(CF₂CF(Z)O)—,or combinations thereof. In these repeating units, p is typically aninteger of 1 to 10. In some embodiments, p is an integer of 1 to 8, 1 to6, 1 to 4, or 1 to 3. The group Z is F, a perfluoroalkyl group,perfluoroether group, perfluoropolyether, or a perfluoroalkoxy group,all of which can be linear, branched, or cyclic. The Z group typicallyhas no more than 12 carbon atoms, no more than 10 carbon atoms, no morethan 9 carbon atoms, no more than 4 carbon atoms, no more than 3 carbonatoms, no more than 2 carbon atoms, or no more than 1 carbon atom. Insome embodiments, the Z group can have no more than 4 oxygen atoms, nomore than 3 oxygen atoms, no more than 2 oxygen atoms, no more than 1oxygen atoms, or no oxygen atoms. In these perfluoropolyetherstructures, the different repeating units can be distributed randomlyalong the chain. Each x independently represents an integer greater thanor equal to 2, and wherein d is an integer from 1 to 8; The numberaverage molecular weight of R_(f) can be from 400 to 5000, in anotherembodiment from 800 to 4000, in yet another embodiment from 1000 to3000. C_(d)F_(2d) can be linear or branched.

Q is independently a connecting group of valence at least 2, including,but not limited to —C(O)NR(CH₂)_(h)—, —C(O)NRCH₂CH(CH₂—)CH₂—,—C(O)NRCH₂CH(CH₂—)₂, —(CH₂)_(h)—, —SO₂NR(CH₂)_(h)—,—(CH₂)_(h)—O—(CH₂)_(j)—, —(CH₂)_(h)—S—(CH₂)_(j)—, —CH₂C[(CH₂—)]₃ whereinR is H or a lower alkyl of 1 to 4 carbon atoms; h is from 1 to 30 and jis from 2 to 20;

A is a (meth)acryl functional group —XC(O)C(R²)═CH₂, wherein R² is alower alkyl of 1 to 4 carbon atoms or H or F, and X is as defined above;

m is at least 1;

n is at least 1;

a is 1 to 6, with the proviso that m+n is 2 to 10, and in which eachunit referred to by the subscripts m and n is attached to an R_(i) unit.

In one embodiment Q can be a straight or branched chain orcycle-containing connecting group. Q can include a covalent bond, analkylene, an arylene, an aralkylene, an alkarylene. Q can optionallyinclude heteroatoms such as O, N, and S, and combinations thereof. Q canalso optionally include a heteroatom-containing functional group such ascarbonyl or sulfonyl for example, and combinations thereof.

By their method of synthesis, these materials are necessarily mixtures.If the mole fraction of isocyanate groups is arbitrarily given a valueof 1.0, then the total mole fraction of m and n units used in makingmaterials of Formula (1) is 1.0 or greater. The mole fractions of m:nranges from 0.95:0.05 to 0.05:0.95. In one embodiment, the molefractions of m:n are from 0.50:0.50 to 0.05:0.95. In another embodiment,the mole fractions of m:n are from 0.25:0.75 to 0.05:0.95 and in yetanother embodiment, the mole fractions of m:n are from 0.25:0.75 to0.10:0.90. In the instances the mole fractions of m:n total more thanone, such as 0.15:0.90, the m unit is reacted onto the isocyanate first,and a slight excess (0.05 mole fraction) of the n units are used.

In an exemplary formulation, for instance, in which 0.15 mole fractionsof m and 0.85 mole fraction of n units are introduced, a distribution ofproducts is formed in which some fraction of products formed contain nom units. There will, however, be present in this product distribution,materials of Formula (1).

Numerous diisocyanates (di-functional isocyanates), modifieddiisocyanate materials, and higher functional isocyanates may be used asR_(i) in the present invention as the residue of multi-isocyanate andstill fall within the scope of the present invention. In one embodiment,multifunctional materials based on hexamethylene diisocyanate (“HDI”)are utilized. One commercially available derivative of HDI is Desmodur™N100, available from Bayer Polymers LLC of Pittsburgh, Pa.

Further, other diisocyanates such as toluene diisocyanate (“TDI”) orisophorone diisocyanate (“IPDI”) may also be utilized as R_(i) in thepresent invention. Non-limiting examples of aliphatic and aromaticisocyanate materials, for example, that may be used include, but are notlimited to, Desmodur™ 3300, Desmodur™ TPLS2294, and Desmodur™ N3600, allobtained from Bayer Polymers LLC of Pittsburgh, Pa.

Materials used to make an additive of Formula (1) may be described bythe Formula: HOQ(A)_(a), and can be exemplified by, for instance,1,3-glycerol dimethacrylate, available from Echo Resins Inc. ofVersailles, Mo.; and pentaerythritol triacrylate, available as SR444Cfrom Sartomer of Exton, Pa.

Typically, the additives of this embodiment can be made by firstreacting the polyisocyanate with the perfluoropolyether—containingalcohol, thiol, or amine, followed by reaction with the hydroxylfunctional multiacrylate, usually in a non-hydroxylic solvent and in thepresence of a catalyst such as an organotin compound. Alternatively, theadditives of this embodiment can be made by reacting the polyisocyanatewith the hydroxyl functional multiacrylate, followed by reaction withthe perfluoropolyether-containing alcohol, thiol, or amine, usually in anon-hydroxylic solvent and in the presence of a catalyst such as anorganotin compound. In addition, the additives could also be made byreacting all three components simultaneously, usually in anon-hydroxylic solvent and in the presence of a catalyst such as anorganotin compound.

A specific example of a compound that fits within Formula (1) is shownbelow:

which is the reaction product of the biuret of HDI with one equivalentof HFPO oligomer amidol (F(CF(CF₃)CF₂O)_(x)CF(CF₃)—C(O)NHCH₂CH₂OH) andfurther with two equivalents of pentaerythritol triacrylate, wherein “x”averages 2 to 15. In some embodiments, x averages between 3 and 10 or xaverages between 5 and 8.

Another specific example of a compound of Formula (1) is

In another embodiment, the fluoro-acrylate-containing additive can be ofFormula (2):

R_(f2)-[Q-(XC(O)NHQOC(O)C(R²)═CH₂)_(a)]_(g)   (Formula 2)

wherein X,Q, and R² are as defined above;

a is from 1 to 6; and

g is 1 or 2;

R_(f2) is either a monovalent perfluoropolyether moiety composed ofgroups comprising the formula F(R_(fc)O)_(x)C_(d)F_(2d)— or a divalentperfluoropolyether moiety composed of groups comprising the formula—C_(d)F_(2d)O(R_(fc)O)_(x)C_(d)F_(2d)—, in which R_(fc), x, and d are asdefined above, and C_(d)F_(2d) can be linear or branched.

R_(f2) can be monovalent or divalent. In some compounds where R_(f2) ismonovalent, the terminal groups can be (C_(p)F_(2p+1))—,(C_(p)F_(2p+1)O)—, (X′C_(p)F_(2p)O)—, or (X′C_(p)F_(2p+1))— where X′ ishydrogen, chlorine, or bromine and p is an integer of 1 to 10. In someembodiments of monovalent R_(f2) groups, the terminal group isperfluorinated and p is an integer of 1 to 10, 1 to 8, 1 to 6, 1 to 4,or 1 to 3. Exemplary monovalent R_(f2) groups includeCF₃O(C₂F₄O)_(x)CF₂—, C₃F₇O(CF₂CF₂CF₂O)_(x)CF₂CF₂—, andC₃F₇O(CF(CF₃)CF₂O)_(x)CF(CF₃)— wherein x has an average value of 0 to50, 1 to 50, 3 to 30, 3 to 15, or 3 to 10.

Exemplary structures for divalent R_(f2) groups include, but are notlimited to, —CF₂O(CF₂O)_(x1)(C₂F₄O)_(x2)CF₂—,—(CF₂)₃O(C₄F₈O)_(x)(CF₂)₃—, —CF₂O(C₂F₄O)_(x)CF₂—,—CF₂CF₂O(CF₂CF₂CF₂O)_(x)CF₂CF₂—, and—CF(CF₃)(OCF₂CF(CF₃))_(x1)OC_(d)F_(2d)O(CF(CF₃)CF₂O)_(x2)CF(CF₃)—,wherein x1 and x2 independently have an average value of 0 to 50, 1 to50, 3 to 30, 3 to 15, or 3 to 10; the sum of x1 and x2 has an averagevalue of 1 to 50 or 4 to 40; and d is an integer of 1 to 8.

In one embodiment, the average molecular weight (number average) ofR_(f2) is 400 to 5000, in another embodiment 800 to 4000, in anotherembodiment 1000 to 3000.

Exemplary HFPO-substituted urethane acrylates of Formula 2 that can beutilized in hardcoat compositions of the invention include the reactionof HFPO-polyols, HFPO-polymercapotan or HFPO-polyamine withCH₂═C(CH₃)C(O)OCH₂CH₂NCO, such as,HFPO—C(O)NHC₂H₄OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂,HFPO—(O)NHC(C₂H₅)(CH₂OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂)₂,HFPO—C(O)NHC₂H₄OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂]₂,HFPO—C(O)NHC(C₂H₅)(CH₂OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂)₂]₂,HFPO—C(O)NHCH₂CH[OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂]CH₂OC(O)NHC₂H₄OC(O)C(CH₃)═CH,HFPO—C(O)NHC(C₂H₅)(CH₂OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂)₂,CH₂═C(CH₃)C(O)OC₂H₄NHC(O)OC₂H₄NHC(O)—HFPO—C(O)NHC₂H₄OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂,HFPO—C(O)NHC₂H₄SC(O)NHC₂H₄OC(O)C(CH₃)═CH₂,CH₂═C(CH₃)C(O)OC₂H₄NHC(O)SC₂H₄NHC(O)—HFPO—C(O)NHC₂H₄SC(O)NHC₂H₄OC(O)C(CH₃)═CH₂,HFPO—C(O)NH(C₂H₄N(C(O)NHC₂H₄OC(O)C(CH₃)═CH₂)₄C₂H₄NHC(O)—HFPO, orcombinations thereof.

In another embodiment, a fluoro-acrylate-additive that can be used in ahardcoat composition of the invention is given by Formula (3):

wherein R_(i), X, R_(f), Q, a, m ,n, and A are as identified before; and

o is at least 1;

G is alkyl, aryl, alkaryl, aralkyl group, substituted alkyl/aryl groupwith functional group or a combination thereof G also optionally hasheteroatom-containing functional groups such as carbonyl, sulfonyl,polyethyleneoxide or combinations thereof. Further, G may have acombination of heteroatoms and heteroatom-containing functional groups.Representative examples of functional groups include, but are notlimited to, —Si(OMe)₃, —(C₂H₄O)_(i)R³, and —CO₂R³; wherein R³ is alklygroup having 1 to 30 carbon atoms, and i is from 5 to 5000;

G optionally contains pendant or terminal reactive groups. The optionalreactive group of G may include (meth)acryl groups, vinyl groups, allylgroups and —Si(OR⁴)₃ groups, where R⁴ is a lower alkyl of 1 to 4 carbonatoms. G also optionally has fluoroalkyl or perfluoroalkyl groups.

HXQG used in making materials of Formula (3) may be monoalcohol,monothiol or monoamine, including, but not limited to, such asn-C₁₂H₂₅OH, n-C₁₈H₃₇OH, n-C₁₈H₃₇O(C₂H₄O)_(i)H, CH₃O(C₂H₄O)_(i)H, whereini is from 5 to 5000, C₄F₉SO₂N(CH₃)CH₂CH₂OH, H₂NCH₂CH₂CH₂(SiOCH₃)₃,HSCH₂CH₂CH₂Si(OCH₃)₃, HO(CH₂)₅CO₂C₂H₄OC(O)CH═CH₂ and HEA(hydroxyethylacrylate). In one embodiment, (m+n+o) is equal to N_(NCO),the number of isocyanate groups originally appended to R_(i). In oneembodiment, and the ratio of (m+n+o)/N_(NCO) may be slightly greaterthan 1, contributed from the excess of n, and in which each unitreferred to by the subscripts m, n, and o is attached to an R_(i) unit.

In another embodiment, an additive that can be used in a hardcoatcomposition of the invention is given by Formula (4), which itselfrepresents a mixture:

wherein R_(f), Q, X, A, R_(i), m, a, and n are as defined above; and

D is a divalent or q-valent isocyanate reactive group containing residuefrom D(XH)_(q), examples of which include alkylene, arylene, alkarylene,fluoroalkylene, perfluoroalkylene, or aralkylene, which can optionallyinclude heteroatoms such as O, N, and S. q is from 2 to 6.

Compounds of Formula 4 can be obtained from the reaction ofR_(i)(NCO)_(m+n+1) with D(XH)₂, such as a diol, dithiol or diamine toform (OCN)_(m+n)R_(i)—NHC(O)X-D-XC(O)NH—R_(i)(NCO)_(m+n), followed bythe reaction with R_(f)-Q-XH and (A)a-Q-OH. Multi-isocyanate reactivechemical, D(XH)_(q), could also been used for making compounds ofFormula 4 by replacing D(XH)₂ with D(XH)_(q). Optionally, HXQG could bepresented in Formula 4.

In this embodiment, when making the polyol, polyamine or polythiolextended polyisocyanate by the addition of D(XH)_(q) toR_(i)(NCO)_(m+n+1), care should be taken in choosing the ratios, thereaction concentration and the amounts of D(XH)_(q) to avoid highlycrosslinked urethane polymer gels. For instance, if a trifunctionalisocyanate is to be used with a multifunctional alcohol, the amount ofmultifunctional alcohol should be limited to avoid forming a gelledcrosslinked network. In one embodiment, the formulation is primarilybased on diols when the number of c in R_(i)(NCO)_(c) is higher than 2,wherein c is equal to m+n+1.

Representative diols of D(XH)_(q), include, but are not limited to, arenon-fluorinated diols such as HO(CH₂)₂OH, HO(CH₂)₄OH, HO(CH₂)₆OH,HO(CH₂)₁₀OH and HO(CH₂)₂O(CH₂)₂OH; fluorinated diols such asHOCH₂(CF₂)₄CH₂OH, C₄F₉SO₂N(CH₂CH₂OH)₂, HFPO—C(O)NHCH₂CH₂CH₂N(CH₂CH₂OH)₂,HOCH₂CH₂NHC(O)—HFPO—C(O)NHCH₂CH₂OH,HOCH₂CH₂NHC(O)—CF₂(OCF₂)_(x1)(CF₂CF₂O)_(x2)CF₂—C(O)NHCH₂CH₂OH,HOCH₂—CF₂(OCF₂)_(x1)(CF₂CF₂O)_(x2)CF₂—CH₂OH,H(OCH₂C(CH₃)(CH₂OCH₂CF₃)CH₂)_(x)OH (Fox-Diol, having a MW about 1342 andavailable from Omnova Solutions Inc. of Akron, Ohio); and functionalizeddiol such as CH₃N(CH₂CH₂OH)₂ and hydantoin hexaacrylate (HHA), preparedas described in Example 1 of U.S. Pat. No. 4,262,072 to Wendling et al,and CH₂═C(CH₃)C(O)OCH₂CH(OH)CH₂O(CH₂)₄OCH₂CH(OH)CH₂OC(O)C(CH₃)═CH₂.

When D contains —C_(d)F_(2d)O(R_(fc)O)_(x)C_(d)F_(2d)—, m can optionallybe zero.

For each of the formulas (i.e. Formulas 1-4) described herein, when X isO, Q is typically not methylene and thus contains two or more carbonatoms. In some embodiments, X is S or NR. In some embodiments, Q is analkylene having at least two carbon atoms. In other embodiments, Q is astraight chain, branched chain, or cycle-containing connecting groupselected from arylene, aralkylene, and alkarylene. In yet otherembodiments, Q is a straight chain, branched chain, or cycle-containingconnecting group containing a heteroatom such as O, N, and S and/or aheteroatom containing functional groups such as carbonyl and sulfonyl.In other embodiments, Q is a branched or cycle-containing alkylene groupthat optionally contains heteroatoms selected from O, N, S and/or aheteroatom-containing functional group such as carbonyl and sulfonyl. Insome embodiments Q contains a nitrogen containing group such as amide.

In another embodiment, a fluoro-acrylate-containing additive with anon-urethane linkage group can be utilized. These compounds have alinking group that can include a divalent group selected from analkylene, arylene, or combinations thereof and optionally containing adivalent group selected from carbonyl, ester, amide, thioester orsulfonamido, and combinations thereof. In other embodiments, the linkinggroup is a sulfur-containing heteroalkylene group containing a divalentgroup selected from carbonyl, ester, amide, thioester or sulfonamido,and combinations thereof. In other embodiments, the linking group is anoxygen-containing heteralkylene group containing a divalent groupselected from carbonyl, ester, thioester, sulfonamido, and combinationsthereof. In yet other embodiments, the linking group is anitrogen-containing heteroalkylene group containing a divalent groupselected from carbonyl, amide, thioester, or sulfonamido, andcombinations thereof.

Exemplary fluoro-acrylate-non-urethane additives that can be used in ahardcoat composition of the invention can be given by Formula (5):

(R_(f2))—[(W)—(R_(A))_(a)]_(g)   (Formula 5)

wherein R_(f2) is a monovalent perfluoropolyether moiety composed ofgroups comprising the formula F(R_(fc)O)_(x)C_(d)F_(2d)—, or divalentperfluoropolyether group composed of groups comprising the formula—C_(d)F_(2d)O(R_(fc)O)_(x)C_(d)F_(2d)— with number average molecularweight about 400 to 5000; in one embodiment about 800 to 4000; and inanother embodiment about 1000 to 3000, wherein R_(fc), d, and x are asdefined above; C_(d)F_(2d) may be linear or branched;

W is a linking group; and

R_(A) is a is a free-radically reactive group such as (meth)acryl,allyl, or vinyl, group; a is 1 to 6, and g is 1 or 2.

As synthesized, compounds according to Formula (5) typically include amixture of R_(f2) groups. The average structure is the structureaveraged over the mixture components. The average molecular weight ofR_(f2) is generally at least about 400. Compounds of Formula (5) oftenhave a molecular weight (number average) of 400 to 5000, 800 to 4000, or1000 to 3000.

The linking group W between the perfluoropolyether segment and(meth)acryl or —COCF═CH₂ endgroup includes a divalent group selectedfrom an alkylene, arylene, heteroalkylene, or combinations thereof andan optional divalent group selected from carbonyl, ester, amide,sulfonamido, or combinations thereof. W can be unsubstituted orsubstituted with an alkyl, aryl, halo, or combinations thereof. The Wgroup typically has no more than 30 carbon atoms. In some compounds, theW group has no more than 20 carbon atoms, no more than 10 carbon atoms,no more than 6 carbon atoms, or no more than 4 carbon atoms. Forexample, W can be an alkylene, an alkylene substituted with an arylgroup, or an alkylene in combination with an arylene or an alkyl etheror alkyl thioether linking group.

The perfluoropolyether acrylate compounds (e.g. of Formula 5) can besynthesized by known techniques such as described in U.S. Pat. Nos.3,553,179 and 3,544,537 as well as U.S. Pat. No. 7,094,829,“Fluorochemical Composition Comprising a Fluorinated polymer andTreatment of a Fibrous Substrate Therewith”.

Exemplary fluoro-acrylate-non-urethane compounds of Formula 5 that canbe utilized in hardcoat compositions of the invention include, but arenot limited to, for exampleHFPO—[C(O)NHCH₂CH₂OCH₂CH₂OCH₂CH₂OC(O)CH═CH₂]_(1˜2),HFPO—[C(O)NH—(CH₂)₆OC(O)CH═CH]_(1˜2),HFPO—[C(O)NHC(CH₂OC(O)CH═CH₂)₃]_(1˜2),HFPO—[C(O)N(CH₂CH₂OC(O)CH═CH₂)₂]_(1˜2),HFPO—[C(O)NHCH₂CH₂N(C(O)CH═CH₂)CH₂OC(O)CH═CH₂]_(1˜2);HFPO—[C(O)NHC(CH₂OC(O)CH═CH₂)₂H]_(1˜2),HFPO—[C(O)NHC(CH₂OC(O)CH═CH₂)₂CH₃]_(1˜2),HFPO—[C(O)NHC(CH₂OC(O)CH═CH₂)₂CH₂CH₃]_(1˜2),HFPO—[C(O)NHCH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂]_(1˜2),HFPO—[C(O)NHCH₂CH₂CH₂N(CH₂CH₂OC(O)CH═CH₂)₂]_(1˜2),HFPO—[C(O)OCH₂C(CH₂OC(O)CH═CH₂)₃]_(1˜2),CH₂═CHC(O)OCH₂CH(OC(O)—HFPO)CH₂OCH₂CH(OH)CH₂OCH₂CH(OC(O)—HFPO)CH₂OCOCH═CH₂,HFPO—CH₂OCH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂, HFPO—CH₂OC(O)CH═CH₂,HFPO—CH₂CH₂OC(O)CH═CH₂, HFPO—CH₂CH₂OC(O)C(CH₃)═CH₂,HFPO—CH₂CH₂OCH₂CH₂OC(O)CH═CH₂,(CH₂═CHC(O)O)CH₂CH(OC(O)C(CH₃)═CH₂)CH₂NHC(O)—HFPO—C(O)NHCH₂CH(OC(O)C(CH₃)═CH₂)CH₂OC(O)C(CH₃)═CH₂,and combinations thereof.

More (per)fluoropolyether acryl compounds described such as in U.S.Publication No. US 2005/0250921A1 and US Publication No. 2005/0249940,incorporated herein by reference.

In other embodiments, the fluoro-acrylate-non-urethane compound may be acompound prepared by Michael-type addition of a reactive(per)fluoropolyether with a poly(meth)acrylate, such as the adduct ofHFPO—C(O)N(H)CH₂CH₂CH₂N(H)CH₃ with trimethylolpropane triacrylate(TMPTA). Such (per)fluoropolyether acrylate compounds are furtherdescribed in U.S. Pat. No. 7,101,618.

Other exemplary fluoro-acrylate-non-urethane compounds that can beutilized in compositions of the invention include those disclosed inU.S. Pat. Nos. 3,810,874 and 4,321,404. A representative compound isgiven by the structureCH₂═CHC(O)OCH₂CF₂O(CF₂CF₂O)_(x1)(CF₂O)_(x2)CH₂OC(O)CH═CH₂,

where x1 and x2 designate that the number of randomly distributedperfluoroethyleneoxy and perfluoromethyleneoxy backbone repeating units,respectively, x1 and x2 have independent values, for example from 1 to50 , and the ratio of x1/x2 is 0.2 to 1 to 5/1.

Still other fluoro-acrylate-non-urethane compounds include vinylcompounds such as HFPO—[C(O)NHCH₂CH═CH₂]_(1˜2), andHFPO—[C(O)NHCH₂CH₂OCH═CH₂]_(1˜2).

These fluoro-acrylate containing additives or thefluoro-acrylate-non-urethane containing additives can both be employedas the sole perfluoropolyether containing additive in a hardcoatcomposition. Alternatively, however, thefluoro-acrylate-urethane-containing additive(s) described herein may beemployed in combination with the fluoro-acrylate-non-urethane containingcompounds. In these embodiments, the two additives can be added to thehardcoat composition such that the weight ratio of thefluoro-acrylate-containing additive to thefluoro-acrylate-non-urethane-additives is 1:1, in one embodiment 2:1 andin another embodiment 3:1. Within these exemplary ratios it is possibleto have the total weight percent fluorine(F) of the curable mixturecomprise from 0.5-25 wt-% F, in one embodiment 0.5 to 10 wt-% F and inanother embodiment 0.5 to 5 wt-% F. In one exemplary additive, theperfluoropolyether moiety of the fluoro-acrylate-containing additive canbe a HFPO moiety and the fluorinated moiety of thefluoro-acrylate-non-urethane additive can be a HFPO.

In one synergistic combination, a perfluoropolyether urethane having aperfluoropolyether moiety and a multi-(meth)acryl terminal group isemployed in combination with a (non-urethane) monofunctionalperfluoropolyether compound having a perfluoropolyether moiety linked toa (meth)acryl group. Typically, the perfluoropolyether moiety is aterminal group of the compound. Likewise, the (meth)acryl group is alsotypically a terminal group. In another embodiment, the second(non-urethane) perfluoropolyether compound typically has a higher weightpercent fluorine than the perfluoropolyether urethane multi-(meth)acrylcompound. It is surmised that the monofunctional perfluoropolyethercompound is the major contributor to the high contact angles; whereasthe perfluoropolyether urethane multi-(meth)acryl compoundcompatibilizes the monofunctional perfluoropolyether compound. Thisinteraction can allow higher concentration of monofunctionalperfluoropolyether compound to be incorporated without phase separation.In yet another embodiment, a perfluoropolyether urethane having aperfluoropolyether moiety and a multi-(meth)acryl terminal group isemployed in combination with a (non-urethane) multi-functionalperfluoropolyether compound having a perfluoropolyether moiety linked toat least two (meth)acryl group. Alternatively, a perfluoropolyetherurethane monoacrylate can be employed in combination with a(non-urethane) mono-or multi-(meth)acryl perfluoropolyether compound.

The fluorocarbon- and urethane (meth)acryl additives (e.g. such as thoseof Formulas (1), (2), (3) or (4), optionally in combination with variousother (per)fluoropolyether (meth)acryl compounds, may also be combinedwith one or more other (non-urethane) fluorinated compounds to improvethe compatibility of the mixture.

In another embodiment a fluoro-acrylate-containing additive of theinvention can be represented by Formula 6:

R_(f3)-J-OC(O)NH—K—HNC(O)O—(C_(b)H_(2b))CH_((3-v))((C_(y)H_(2y))OC(O)C(R²)═CH₂)_(v)  (Formula 6)

wherein, R_(f3) is a monovalent perfluoroalkyl group or apolyfluoroalkyl group which can be linear, branched, or cyclic.Exemplary R_(f3) includes, but not limited to, C_(d)F_(2d+1)—, wherein dis 1 to 8; CF₃CF₂CF₂CHFCF₂—; CF₃CHFO(CF₂)₃—; (CF₃)₂NCF₂CF₂—;CF₃CF₂CF₂OCF₂CF₂—; CF₃CF₂CF₂OCHCF₂—; n-C₃F₇OCF(CF₃)—; H(CF₂CF₂)₃—; non-C₃F₇OCF(CF₃)CF₂OCF₂—.

J is a divalent linkage group, selected from, but not limited to,

-   -   R is H or an alkyl group of 1 to 4 carbon atoms;    -   h is 1 to 30;    -   j is 2 to 10;

K is the residue of a diisocyanate with an unbranched symmetric alkylenegroup, arylene group, or aralkylene group. Exemplary K includes, but isnot limited to, —(CH₂)₆—,

b is 1 to 30;

y is 1 to 5;

v is 1 to 3; and

R² is H, CH₃, or F.

In one embodiment, R_(f3) is a perfluoroalkyl group that includes atleast one heteroatom, or a polyfluoroalkyl group that includes at leastone heteroatom. Examples of heteroatoms that can be included in eitherthe perfluoroalkyl groups or polyfluroalkyl groups include, but are notlimited to, O and N. Specific examples of possible perfluoroalkylgroups, polyfluoroalkyl groups, perfluroalkyl groups including at leastone heteroatom, and polyfluoroalkyl groups including at least oneheteroatom include, but are not limited to, C_(d)F_(2d+1), wherein d is1 to 8; CF₃CF₂CF₂CHFCF₂—; CF₃CHFO(CF₂)₃—; (CF₃)₂NCF₂CF₂—;CF₃CF₂CF₂OCF₂CF₂—; CF₃CF₂CF₂OCHCF₂—; n-C₃F₇OCF(CF₃)—; H(CF₂CF₂)₃—; orn-C₃F₇OCF(CF₃)CF₂OCF₂—.

In one embodiment J is

In another embodiment J is

where h is 2 to 4.

In another embodiment J is

In one embodiment, K is

In another embodiment, K is

In one embodiment, b is 2 to 12; in another embodiment, b is 2, 4, 6,10, or 12; in yet another embodiment, b is 2, 4, or 12.

In one embodiment, R² is H.

In one embodiment, v is 1 or 3.

Specific fluoro-acrylate-additives of Formula 6 useful in hardcoatcompositions of the invention may include, but are not limited to,C₄F₉SO₂N(CH₃)C₂H₄O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(MeFBSE-MDI-HEA),C₄F₉SO₂N(CH₃)C₂H₄O—C(O)NH(CH₂)₆NHC(O)—OC₂H₄OC(O)Me=CH₂(MeFBSE-HDI-HEMA),C₄F₉SO₂N(CH₃)C₂H₄O—C(O)NH(CH₂)₆NHC(O)—OC₄H₈OC(O)CH═CH₂(MeFBSE-HDI-BA),C₄F₉SO₂N(CH₃)C₂H₄O—C(O)NH(CH₂)₆NHC(O)—OC₁₂H₂₄OC(O)CH═CH₂(MeFBSE-HDI-DDA), CF₃CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(CF₃CH₂OH-MDI-HEA), C₄F₉CH₂CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₄F₉CH₂CH₂OH-MDI-HEA),C₆F₁₃CH₂CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₆F₁₃CH₂CH₂OH-MDI-HEA),C₃F₇CHFCF₂CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₃F₇CHFCF₂CH₂OH-MDI-HEA),CF₃CHFO(CF₂)₃CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(CF₃CHFO(CF₂)₃CH₂O-MDI-HEA),C₃F₇OCHFCF₂CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₃F₇OCHFCF₂CH₂OH-MDI-HEA),C₃F₇OCF(CF₃)CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₃F₇OCF(CF₃)CH₂OH-MDI-HEA),C₄F₉SO₂NMeC₂H₄O—C(O)NHC₆H₄CH₂C₆H₄NHC(O)—OCH₂C(CH₂OC(O)CH═CH₂)₃(MeFBSE-MDI-(SR-444C)), and combinations thereof. The preparation offluoro-acrylate-additives of Formula 6 has been described in U.S.Publication No. US 2005/0143541A1, incorporated herein by reference.

These fluoro-acrylate-additives of the invention can be prepared, forexample, by first combining a fluorochemical alcohol and an unbranchedsymmetric diisocyanate in a selected solvent, and then adding ahydroxy-terminated alkyl (meth)acrylate. Useful solvents include, butare not limited to, aromatic solvents (for example, toluene), aliphaticsolvent such as hexane, heptane, pentane, cyclic pentane and cyclichexane; fluorinated solvent such as C₄F₉OCH₃, C₄F₉OCH₂CH₃ and C₃F₇OCH₃,or combinations thereof.

Generally, the reaction mixture can be agitated. The reaction cangenerally be carried out at a temperature between room temperature andabout 120° C.; in one embodiment, the reaction can be carried out atbetween 30° C. and 70° C. for improved selectivity.

Typically the reaction can be carried out in the presence of a catalyst.Useful catalysts include, but are not limited to, bases (for example,tertiary amines, alkoxides, and carboxylates), metal salts and chelates,organometallic compounds, acids and urethanes. In one embodiment, thecatalyst is an organotin compound (for example, dibutyltin dilaurate(DBTDL) or a tertiary amine (for example, diazobicyclo[2.2.2]octane(DABCO)), or a combination thereof. In another embodiment, the catalystis DBTDL.

Fluorochemical alcohols that are useful to formfluoro-acrylate-additives of the invention can be represented by formula7:

R_(f3)-J-OH   Formula 7

wherein R_(f3) is a perfluoroalkyl group or a polyfluoroalkyl group, Jis a divalent linkage group, selected from, but not limited to,

R is hydrogen or an alkyl group of 1 to 4 carbon atoms;

h is 1 to 30; and

j is 2 to 10;

In one embodiment, R_(f3) is a perfluoroalkyl group that includes atleast one heteroatom, or a polyfluoroalkyl group that includes at leastone heteroatom. Examples of heteroatoms that can be included in eitherthe perfluoroalkyl groups or polyfluroalkyl groups include, but are notlimited to, O and N. Specific examples of possible perfluoroalkylgroups, polyfluoroalkyl groups, perfluroalky groups including at leastone heteroatom, and polyfluoroalkyl groups including at least oneheteroatom include, but are not limited to, C_(d)F_(2d+1), wherein e is1 to 8; CF₃CF₂CF₂CHFCF₂—; CF₃CHFO(CF₂)₃—; (CF₃)₂NCF₂CF₂—;CF₃CF₂CF₂OCF₂CF₂—; CF₃CF₂CF₂OCHCF₂—; n-C₃F₇OCF(CF₃)—; H(CF₂CF₂)₃—; orn-C₃F₇OCF(CF₃)CF₂OCF₂—.

In one embodiment, d is 1 to 8; in another embodiment, d is 4 to 6.

In one embodiment, h is 2 to 4.

In one embodiment, J is

In another embodiment J is

where j is 2 to 4. In another embodiment J is

In yet another embodiment J is

In one embodiment, fluorochemical alcohols that can be utilized to formfluoro-acrylate-additives of the invention include, but are not limitedto, C₄F₉SO₂NCH₃(CH₂)₂OH, C₄F₉SO₂NCH₃(CH₂)₄OH, and C₄F₉(CH₂)₂OH. Inanother embodiment, the fluorochemical alcohol is C₄F₉SO₂NCH₃(CH₂)₂OH.

Representative examples of suitable alcohols include, but are notlimited to, CF₃CH₂OH, (CF₃)₂CHOH, (CF₃)₂CFCH₂OH, C₂F₅SO₂NH(CH₂)₂OH,C₂F₅SO₂NCH₃(CH₂)₂OH, C₂F₅SO₂NCH₃(CH₂)₄OH, C₂F₅SO₂NC₂H₅(CH₂)₆OH,C₂F₅(CH₂)₄OH, C₂F₅CONH(CH₂)₄OH, C₃F₇SO₂NCH₃(CH₂)₃OH, C₃F₇SO₂NH(CH₂)₂OH,C₃F₇CH₂OH, C₃F₇CONH(CH₂)₈OH, C₄F₉SO₂NCH₃(CH₂)₂OH, C₄F₉CONH(CH₂)₂OH,C₄F₉SO₂NCH₃(CH₂)₄OH, C₄F₉SO₂NH(CH₂)₇OH, C₄F₉SO₂NC₃H₇(CH₂)₂OH,C₄F₉SO₂NC₄H₉(CH₂)₂OH, C₅F₁₁SO₂NCH₃(CH₂)₂OH, C₅F₁₁CONH(CH₂)₂OH,C₅F₁₁(CH₂)₄OH, C_(d)F_(2d+1)(CH₂)₂OH, C_(d)F_(2d+1)(CH₂)₂O(CH₂)₂OH,C_(d)F_(2d+1)(CH₂)₂S(CH₂)₂OH, wherein d is 1 to 8; CF₃CF₂CF₂CHFCF₂OH,CF₃CHFO(CF₂)₃OH, (CF₃)₂NCF₂CF₂OH, CF₃CF₂CF₂OCF₂CF₂OH, CF₃CF₂CF₂OCHCF₂OH,n-C₃F₇OCF(CF₃)OH, H(CF₂CF₂)₃)OH, or n-C₃F₇OCF(CF₃)CF₂OCF₂OH.

Representative examples of unbranched symmetric diisocyanates that canbe utilized to form fluoro-acrylate-additives of the invention, include,but are not limited to, 4,4′-diphenylmethane diisocyanate (MDI),1,6-hexamethylene diisocyanate (HDI), 1,4-phenylene diisocyanate (PDI),1,4-butane diisocyanate (BDI), 1,8-octane diisocyanate (ODI),1,12-dodecane diisocyanate, and 1,4-xylylene diisocyanate (XDI). In oneembodiment, unbranched symmetric diisocyanates include, but are notlimited to, MDI, HDI, and PDI. In another embodiment the unbranchedsymmetric diisocyanate that is utilized is MDI. In its pure form, MDI iscommercially available as Isonate™ 125M from Dow Chemical Company(Midland, Mich.), and as Mondur™ from Bayer Polymers (Pittsburgh, Pa.).

Hydroxy-terminated alkyl (meth)acrylates that are useful to formfluoro-acrylate-additives of the invention can have from 2 to 30 carbonatoms. In another embodiment, hydroxyl-terminated alkyl (meth) acrylatesthat have from 2 to 12 carbon atoms in their alkylene portion areutilized.

In one embodiment, the hydroxy-terminated alkyl (meth)acrylate monomeris a hydroxy-terminated alkyl acrylate. In one embodimenthydroxy-terminated alkyl acrylates include, but are not limited to,hydroxy ethyl acrylate, hydroxy butyl acrylate, hydroxy hexyl acrylate,hydroxy decyl acrylate, hydroxy dodecyl acrylate,HOCH₂—C₆H₁₀—CH₂OC(O)CR═CH₂ and HO(CH₂)₅C(O)OCH₂CH₂OC(O)CH═CH₂, andmixtures thereof. In another embodiment, the hydroxyl-terminated alkylmeth(acrylate) monomer is a triacrylate such as pentaerythritoltriacrylate, referred to herein as SR444C, available from SartomerCompany.

One exemplary combination to form fluoro-acrylate-additives of theinvention includes the reaction of fluorochemical alcohols representedby the formula C_(d)F_(2d+1)SO₂NCH₃(CH₂)_(h)OH, wherein d=2 to 5, andh=2 to 4, are reacted with MDI, the process described in U.S. Pat. No.7,081,545, entitled “Process For Preparing FluorochemicalMonoisocyanates”, can be used.

The hardcoat composition that ultimately forms from the hardcoat layeralso includes infrared light absorbing particles. In one embodiment, theinfrared light absorbing particles are chosen to create an article withan acceptable level of haze. Generally, particles in an optical layerbegin to have an effect on haze as the particles increase in size. Inone embodiment, particles that are a factor of 10× smaller than therelevant wavelengths (i.e. visible light) will not impact the haze ofthe layer to an unacceptable degree. In one embodiment, an article withhaze values below 5% is generally considered acceptable.

In one embodiment, the infrared light absorbing particles include metaloxide particles. Oxide nanoparticles are typically colored and absorb inthe different portions of the electromagnetic spectrum. It can bedesirable for a solar control article to have high visible lighttransmission while rejecting as much infrared radiation as possible.Infrared radiation generally refers to electromagnetic radiation between780 nm and 2500 nm. In one embodiment, the concentration of metal oxidenanoparticles (such as those exemplified below) is generally chosen suchthat near 100% extinction is achieved at wavelengths higher than 1800nm; an in another embodiment 100% extinction is achieved at wavelengthshigher than 1500 nm. At such concentrations, visible light transmissionof at least 50% is desired; and in another embodiment visible lighttransmission of at least 70% is desired.

Exemplary metal oxide nanoparticles that can be used as infraredabsorbing particles in hardcoat compositions of the invention include,but are not limited to tin, antimony, indium and zinc oxides and dopedoxides. In some embodiments, the metal oxide nanoparticles include, tinoxide, antimony oxide, indium oxide, indium doped tin oxide, antimonydoped indium tin oxide, antinomy tin oxide, antimony doped tin oxide ormixtures thereof. In some embodiments, the metal oxide nanoparticlesinclude tin oxide or doped tin oxide and optionally further includesantimony oxide and/or indium oxide. The nanoparticles can have anyuseful size such as, for example, 1 to 100, or 30 to 100, or 30 to 75nanometers. In some embodiments, the metal oxide nanoparticles includeantimony tin oxide or doped antimony tin oxide dispersed in a polymericmaterial.

In one embodiment, hardcoat compositions of the invention include asufficient amount of infrared particles to provide an article thatdelivers the desired amount of infrared absorption. In one embodiment,the infrared absorbing particles are present in a range from 20 to 65wt-%. In another embodiment, the infrared absorbing particles arepresent in a range from 20 to 55 wt-%.

To facilitate curing, polymerizable compositions according to theinvention also include at least one initiator. Initiators useful in theinvention include both free-radical thermal initiator and/orphotoinitiator. Typically, an initiator and/or photoinitiator arepresent at less than 10 wt-%, in one embodiment less than 5 wt-%, and inanother embodiment, less than 2 wt-% of the hardcoat composition.Free-radical curing techniques are well known in the art and include,for example, thermal curing methods as well as radiation curing methodssuch as electron beam or ultraviolet radiation. Further detailsconcerning free radical thermal and photopolymerization techniques maybe found in, for example, U.S. Pat. No. 4,654,233 (Grant et al.); U.S.Pat. No. 4,855,184 (Klun et al.); and U.S. Pat. No. 6,224,949 (Wright etal.).

Useful free-radical thermal initiators include, for example, azo,peroxide, persulfate, and redox initiators, and combinations thereof.

Useful free-radical photoinitiators include, for example, those known asuseful in the UV cure of acrylate polymers. Such initiators include, butare not limited to, benzophenone and its derivatives; benzoin,alpha-methylbenzoin, alpha-phenylbenzoin, alpha-allylbenzoin,alpha-benzylbenzoin; benzoin ethers such as benzil dimethyl ketal(commercially available under the trade designation “IRGACURE 651” fromCiba Specialty Chemicals Corporation of Tarrytown, N.Y.), benzoin methylether, benzoin ethyl ether, benzoin n-butyl ether; acetophenone and itsderivatives such as 2-hydroxy-2-methyl-1-phenyl-1-propanone(commercially available under the trade designation “DAROCUR 1173” fromCiba Specialty Chemicals Corporation) and 1-hydroxycyclohexyl phenylketone (commercially available under the trade designation “IRGACURE184”, also from Ciba Specialty Chemicals Corporation);2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanonecommercially available under the trade designation “IRGACURE 907”, alsofrom Ciba Specialty Chemicals Corporation);2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanonecommercially available under the trade designation “IRGACURE 369” fromCiba Specialty Chemicals Corporation); aromatic ketones such asbenzophenone and its derivatives and anthraquinone and its derivatives;onium salts such as diazonium salts, iodonium salts, sulfonium salts;titanium complexes such as, for example, that which is commerciallyavailable under the trade designation “CGI 784 DC”, also from CibaSpecialty Chemicals Corporation); halomethylnitrobenzenes; and mono- andbis-acylphosphines such as those available from Ciba Specialty ChemicalsCorporation under the trade designations “IRGACURE 1700”, “IRGACURE1800”, “IRGACURE 1850”,“IRGACURE 819” “IRGACURE 2005”, “IRGACURE 2010”,“IRGACURE 2020” and “DAROCUR 4265”. Combinations of two or morephotoinitiators may also be used. Further, sensitizers such as2-isopropyl thioxanthone, commercially available from First ChemicalCorporation, Pascagoula, Miss., may be used in conjunction withphotoinitiator(s) such as ““IRGACURE 369”.

The polymerizable coating composition for use as the surface layer orunderlying hardcoat layer may also include other materials as required,such as for better coating and improved performance to meet therequirements for different application. In one embodiment, one or morehindered amine light stabilizer(s) (HALS) and/or one or more phosphonatestabilizer compound(s) may be added in the polymerizable coatingcomposition, as described in U.S. Pat. No. 6,613,819, “Light StableArticles” assigned to 3M Co.

The presence of one or mixed solvents can be desirable for the coatingformulation, especially when metal oxide nanoparticles are present. Theorganic solvent used in the free radical crosslinking reaction can beany organic liquid that is inert to the reactants and product, and thatwill not otherwise adversely affect the reaction, but should help tomake the formulation stable and the coating in high quality. Suitableorganic solvents are polar, including alcohols, such as methanol,ethanol, carbitol and isopropanol, esters, such as ethyl acetate,aromatic solvents such as toluene, ethers such as diethyl ether, THF andt-butyl methyl ether, and ketones, such as acetone and methyl isobutylketone. Other solvent systems may also be used, such as acetonitrile,N,N-dimethylformaide and dimethyl sulfone. The amount of solvent cangenerally be about 20 to 90 percent by weight of the total weight ofreactants and solvent.

The coating formulation can also include other inorganic particles thatcan optionally be incorporated in order to decrease static associatedwith the layer. Generally, metal oxides can be utilized to provide suchproperties. The metal oxides can also be surface treated with materialssuch as 3-methacryloxypropyltrimethoxysilane. These particles canprovide constructions with antistatic properties and other desirableproperties. This can be desirable to prevent static charging andresulting contamination by adhesion of dust and other unwanted debrisduring handling and cleaning of the film. In one such embodiment, suchmetal oxide particles are incorporated into the top (thin) layer oftwo-layer embodiments of this invention, in which the fluoroacrylatecontaining hardcoat is applied to a hydrocarbon-based hardcoat. At thelevels at which such particles may be needed in the coating in order toconfer adequate antistatic properties (typically 25 wt % and greater),these deeply colored particles can impart undesired color to theconstruction. However, in the thin top layer of a two-layer fluorinatedhardcoat construction, their effect on the optical and transmissionproperties of the film can be minimized. Examples of conducting metaloxide nanoparticles useful in this embodiment include antimony doubleoxide available from Nissan Chemical under the trade designations CelnaxCXZ-210IP and CXZ-210IP-F2. When these particles are included atappropriate levels in the coatings of this invention, the resultingfluorinated hardcoats can exhibit static charge decay times less thanabout 0.5 sec. In this test, the sample is placed between two electricalcontacts and charged to ±5 kV. The sample is then grounded, and the timenecessary for the charge to decay to 10% of its initial value ismeasured and recorded as the static charge decay time. In contrast, filmconstructions containing no conducting nanoparticles exhibit staticcharge decay times >30 sec.

As mentioned previously, an article of the invention can optionallyinclude an intermediate adhesive layer 270. The intermediate adhesivelayer 270 can be formed of any useful material. In some embodiments, theintermediate adhesive layer 270 can include a pressure sensitiveadhesive material, as described above. In some embodiments, theintermediate adhesive layer 270 can include a curable adhesive such as,for example a thermal, UV, or moisture curable adhesive. Theintermediate adhesive layer 270 can have any useful thickness such as,for example, 1 to 100 micrometers, or 5 to 50 micrometers, or 10 to 50micrometers, or 10 to 30 micrometers.

The optional intermediate polymeric layer 260 can be formed of anyuseful material. In some embodiments, the intermediate polymeric layer260 can include a polyolefin, polyacrylate, polyester, polycarbonate,fluoropolymer, and the like. In one embodiment, the intermediatepolymeric layer 260 can include a polyethylene terephthalate. Theintermediate polymeric layer 260 can have any useful thickness such as,for example, 5 to 500 micrometers, or 10 to 100 micrometers, or 25 to 75micrometers, or 25 to 50 micrometers.

An article of the invention can also include a tear resistant film (notshown). In many embodiments, the tear resistant film includesalternating layers of stiff polymer and a ductile polymer. In someembodiments, the tear resistant film 160 includes alternating layers ofstiff polyester or copolyester and a ductile sebacic acid basedcopolyester. In many embodiments, the stiff polyester or copolyesterlayers are oriented in at least one direction and, or are biaxiallyoriented. Examples of these tear resistant films are described in U.S.Pat. No. 6,040,061; U.S. Pat. No. 5,427,842; and U.S. Pat. No. 5,604,019which are incorporated by reference herein to the extent they do notconflict with the present disclosure.

In another embodiment, the tear resistant film is a single monolithicpolymeric film that provides a desired level of tear resistance. Suchfilms are known in the art as “tough” polymeric film. Toughness can bedescribed as a measure of the energy a polymer can absorb before itbreaks, and examples of tough polymers include ABS (poly (acrylonitrilebutadiene styrene)), LDPE (linear low density polyethylene), HIPS (highimpact polystryrene), polyurethanes and the like. Additionally,increasing the thickness of the monolithic polymeric film may permit theusage of some polymers, such as PET and nylon, to be utilized as a tearresistant film.

By “tear resistant” it is broadly meant that a multilayer film accordingto this disclosure demonstrates a Graves area in one direction of thefilm which exceeds the Graves area in the same direction for a singlelayer film comprising only the stiff polymer of the multilayer film, thesingle layer film being processed in the same manner as and tosubstantially the same thickness as the multilayer film. In manyembodiments, the tear resistant solar control films demonstrate a Gravesarea in one direction of the film equal to at least about 40+0.4(x) kpsi% wherein x is the nominal thickness of the film in micrometers. Morespecifically, Graves area is obtained by mathematically integrating thearea beneath the curve in a graphical plot of the stress (as measured inkpsi) experienced by the film versus the strain (as measured by Graveselongation in % which is defined more fully below) that the filmundergoes during a test in which a film sample specifically shaped forthe Graves area test is clamped between opposed jaws that are movedapart at a constant rate to concentrate the tearing stresses in a smallarea. Thus, Graves area is a combined measure of the film's tensilemodulus (i.e., the film's stiffness and dimensional stability) and theability of the film to resist advancing a tear. Consequently, Gravesarea may be regarded as a measure of the total energy required to causethe film to fail; that is, the ability of the film to absorb energy. Inmany embodiments, the tear resistant solar control films desirablyexhibit a Graves elongation at break of at least 20%, or at least 40%during the Graves area test. The tear resistance solar control films maybe measured by ASTM Test Method D 1004 (also known as a Graves teartest).

In addition, many multilayer or monolithic tear resistant filmsaccording to this disclosure demonstrate a tensile modulus (as measuredin a conventional tensile test) of at least 175 kpsi (1,208 MPa), or atleast 240 kpsi (1,656 MPa), or at least 450 kpsi (3,105 MPa) in at leastone direction of the film.

Both the thickness of the tear resistant multilayer film and theindividual layers which comprise the tear resistant multilayer film mayvary over wide limits. These films can have a nominal thickness of fromabout 7 to 500 micrometers, or from about 15 to 185 micrometers. Theindividual layers of stiff polyester or copolyester can have an averagenominal thickness of at least about 0.5 micrometers, or from greaterthan 0.5 to 75 micrometers, or from about 1 to 25 micrometers. In someembodiments, the ductile sebacic acid based copolyester layers arethinner than the stiff polyester/copolyester layers. The ductilematerial layers may range in average nominal thickness from greater thanabout 0.01 micrometer to less than about 5 micrometers, or from about0.2 to 3 micrometer. Similarly, the exact order of the individual layersis not critical. The total number of layers may also vary substantially.In many embodiments, the tear resistant multilayer film includes atleast 3 layers, or from 5 to 35 layers, or from 10 to 15 layers.

Experimental A. Materials

Unless otherwise noted, as used in the examples, “HFPO—” refers to theend group F(CF(CF₃)CF₂O)_(x)CF(CF₃)— of the methyl esterF(CF(CF₃)CF₂O)xCF(CF₃)C(O)OCH₃, can be prepared according to the methodreported in U.S. Pat. No. 3,250,808 (Moore et al.), the disclosure ofwhich is incorporated herein by reference, with purification byfractional distillation. “—HFPO—” refers toCH₃(O)CCF(CF₃)(OCF₂CF(CF₃))_(x1)OCF₂CF₂CF₂CF₂O(CF(CF₃)CF₂O)_(x2)CF(CF₃COOCH₃(CH₃O(O)C—HFPO—C(O)OCH₃) prepared from the oligomerization ofFC(O)CF₂CF₂C(O)F with hexafluoropropeneoxide in the presence of KF orCsF as an initiator according to the method reported in U.S. Pat. No.3,250,807 (Fritz, et al.) which provides the HFPO oligomer bis-acidfluoride, followed by methanolysis and purification by removal of lowerboiling materials by fractional distillation as described in U.S. Pat.No. 6,923,921 (Flynn, et. al.). The disclosure of both aforementionedpatents are incorporated herein by reference.

HFPO—OH, HFPO—C(O)NHCH₂CH₂OH, prepared in according to published patent,described in paragraph [0058], US 20060148350 from HFPO—C(O)OCH₃ andNH₂CH₂CH₂OH. The average molecule weight is about 1344. HFPO-Diol,HOCH₂CH₂NHC(O)—HFPO—C(O)NHCH₂CH₂OH, prepared in according to filedpatent, Preparation No. 27 of U.S. patent application Ser. No.11/277,162, filed on Mar. 22, 2006 entitled “PERFLUOROPOLYETHER URETHANEADDITIVES HAVING (METH)ACRYL GROUPS AND HARD COATS”, fromCH₃O(O)C—HFPO—C(O)OCH₃ and NH₂CH₂CH₂OH. A 200 ml round bottom flaskequipped with magnetic stir bar was charged with 3.81 g (0.0624 mol)ethanolamine and heated to 75 degrees Celsius under a dry air. A chargeof 30.0 g (0.240 mol, 1250 MW) CH₃O(O)C—HFPO—C(O)OCH₃ was added via apressure equalizing funnel over 40 min and the reaction was allowed toheat for about 18 h. From Fourier Transform Infrared Spectroscopy (FTIR)analysis, the amide —C(O)NH— was formed as the ester signal (—CO₂—)disappeared. Next 50.7 g of methyl t-butyl ether was added to thereaction to provide a solution that was washed successively with 20 mlof 2N aqueous HCI, and then 3 times with 20 ml of water, The solutionwas then dried over anhydrous magnesium sulfate, filtered andconcentrated on a rotary evaporator at aspirator pressure in a 75degrees Celsius water bath to provide the product as a thick syrup. Theaverage molecule weight is about 1308.

N100, Polyisocyanate Desmodur™ (Des) N100, was obtained from BayerPolymers LLC, of Pittsburgh, Pa.

N3300, Polyisocyanate Desmodur™ 3300, was obtained from Bayer PolymersLLC, of Pittsburgh, Pa.

SR444C, Pentaerythritol triacrylate (“PET3A”), under the tradedesignation “SR444C”, was obtained from Sartomer Company of Exton, Pa.

SR351, Trimethylolpropane triacrylate (“TMPTA”), under the tradedesignation “SR3551”, was obtained from Sartomer Company of Exton, Pa.

NH₂Si, H₂NCH₂CH₂CH₂Si(OCH₃)₃ is available from Sigma Aldrich ofMilwaukee, Wis.

D-1173, Darocur™ 1173 which refers to2-hydroxy-2-methyl-1-phenyl-propan-1-one=photo-cleavage initiator, andis manufactured by Ciba Specialty Chemicals.

I-184, the UV photoinitiator, 1-hydroxycyclohexyl phenyl ketone used wasobtained from Ciba Specialty Products, Tarrytown, N.Y. and sold underthe trade designation “Irgacure 184.”

I-907, the photoinitiator2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one used wasobtained from Ciba Specialty Products, Tarrytown, N.Y. and sold underthe trade designation “Irgacure 907.”

Methyl perfluorobutyl ether (HFE 7100 or 4O1) was obtained from 3MCompany, St. Paul, Minn.

DBTDL, Dibutyltin dilaurate was obtained from Sigma Aldrich ofMilwaukee, Wis.

Unless otherwise noted, “MW” refers to molecular weight and “EW” refersto equivalent weight. Further, “° C.” may be used interchangeably with“degrees Celsius” and “mol” refers to moles of a particular material and“eq” refers to equivalents of a particular material. Further, “Me”constitutes a methyl group and may be used interchangeably with “CH₃.”

ATO-1, refers to an antimony tin oxide (ATO) coating formulation thatincludes 62.5% ATO (from Inframat Corporation), 15% HDDA (1,6-hexanediol diacrylate, SR238 from Sartomer), 15% PETA (Pentaerythritoltriacrylate, PETA-K from UCB-Radcure), and 7.5% polymeric dispersant(Solplus D510 from Noveon Inc., Cleveland Ohio.). The dispersion wasmilled for 8 hours using Netzsch LME-1 Disk Mill with MoliNEX™ eccentricdisks and one liter stainless steel chamber (Netzsch Incorporated, ExtonPa.). The final particle size was ˜60 nm (PDI=0.21) measured byZetasizer Nano ZS (Malvern Instruments Ltd, Worcestershire, UnitedKingdom). ATO-1 was then made by making a 45% solution of theformulation in 1-methoxy2-propanol. The solution was diluted to 30%formulation with methyl isobutyl ketone, and 2% Darocur™ 1173 (CibaSpecialty Chemicals, Tarrytown N.Y.) photo initiator was added.

ATO-2, refers to an ATO coating formulation included 80 g TRB Paste 6070(purchased from Advanced Nano Products, S. Korea); and 20 g ATO premixformulation that includes: 24.58% HDDA, 1.59% Tinuvin 123, 1.11%Irgacure 819, 1.11% Irgacure 184, 0.26% FA-1, and 71.36% MEK.

Solvent isopropane alcohol (IPA), methyl ethyl ketone (MEK), toluene,methyl isobutyl ketone (MIBK), acetone, ethyl acetate (EtOAc) andN,N-dimethylformamide (DMF) are available from Aldrich;

MeFBSEA, C₄F₉SO₂NMeC₂H₄OC(O)CH═CH₂, prepared according to the proceduredescribed in Example 2-B, WO 01/130973, available from 3M Co.

B. Preparation of Additives Preparation of FA-1, HFPO—OH/N100/SR-444C(15/100/88.5)

A 500 ml round bottom 2-necked flask equipped with magnetic stir bar wascharged with 25.00 g (0.131 eq, 191 EW) Des N100, 26.39 g (0.0196 eq,1344 EW) F(CF(CF₃)CF₂O)_(6.85)CF(CF₃)C(O)NHCH₂CH₂OH, and 109.62 g MEK,and was swirled to produce a homogeneous solution. The flask was placedin an 80 degrees Celsius bath, charged with 2 drops of dibutyltindilaurate catalyst, and fitted with a condenser. The reaction was cloudyat first, but cleared within two minutes. At about 1.75 hours, the flaskwas removed from the bath and 2.42 g of MEK was added to compensate forlost solvent. A 2.0 g sample was removed from the flask, leaving(1-(2.0/161.01) or 0.9876 weight fraction, of the reaction, and 57.51 g(98.76% of 58.23 g) (0.116 mol, 494.3 equivalent weight) SR-444C wasadded to the reaction, which was placed in a 63 degrees Celsius bath. Atabout 5.25 hours FTIR showed no isocyanate absorption at 2273 cm⁻¹, and0.56 g MEK was added to compensate for solvent lost to bring thematerial to 50% solids. The product has a calculated wt % F of 15.6% F.

Preparation of FA-2, HFPO—OH/N100/SR-444C/NH₂Si (5/30/20/5)

A 500 ml round bottom flask equipped with a stir bar was charged with5.73 g (30 meq) Des N100, 37 g MEK, 15 g C₄F₉OCH₃, 2 drops of DBTDL,6.15 g (5 meq) HFPO—C(O)NHCH₂CH₂OH (1229 equivalent molecule weight),and 0.05 g BHT, and placed in a 60 degrees Celsius oil bath. After 1hour, 0.98 g (5 meq) H₂N(CH₂)₃Si(OCH₃)₃ was added, followed in 10minutes by the addition of 4.46 g (20 meq, 494.3 equivalent weight)SR444C. The reaction mixture showed no residual isocyanate by FTIR aftera total reaction time of 5.75 hours at 25% solution.

Preparation of FA-3, HFPO—OH/N100/SR-444C (15/100/85)

A 500 ml round bottom flask equipped with magnetic stir bar was chargedwith 25.0 g (100 mole percent) (0.131 eq, 191 EW) Des N100, 55.5 g (85mole percent) (0.087 eq, 494.3 EW) of Sartomer SR444C, 11.5 mg (15 molepercent) of MEHQ, and 126.77 g methyl ethyl ketone (MEK). The reactionwas swirled to dissolve all the reactants, the flask was placed in anoil bath at 60 degrees Celsius, and fitted with a condenser under dryair. Two drops of dibutyltin dilaurate was added to the reaction. After1 hour, 58.64 g (0.0436 eq, 1344 EW)F(CF(CF₃)CF₂O)_(6.85)CF(CF₃)C(O)NHCH₂CH₂OH was added to the reaction viaaddition funnel over about 75 minutes. The reaction was monitored byFTIR and showed a small isocyanate absorption at 2273 cm⁻¹ after about 5hours of reaction, but no isocyanate absorption at 7.5 hours ofreaction. The material was used as a 50% solids solution in MEK.

Preparation of FA-4, HFPO-Diol/N3300/SR-444C (5/30/20)

A 240 ml bottle was charged with 5.79 g Des N3300 (EW about 193, about30 milliequivalents NCO), 3.35 g HFPO-Diol (MW about 1341, 10 meq OH),9.89 g SR-444C (EW about 494.3, about 20 milliequivalents OH), 5 dropsof dibutyltin dilaurate catalyst and 52 g MEK (about 30% solid) undernitrogen. The solution was reacted at 70 degrees Celsius in an oil bathwith a magnetic stir bar for 10 hours after sealing the bottle. Therewas a small amount of precipitate formed upon standing at roomtemperature. FTIR analysis showed no unreacted-NCO signal.

FA-5, an approximately 1:1 molar ratio adduct ofHFPO—C(O)NHCH₂CH₂CH₂NHCH₃ and TMPTA was prepared according to theprocedure described in paragraph [0110], U.S. Pat. No. 7,101,618.

Preparation of FC-6, HFPO—C(O)N(H)CH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂

FA-6 was prepared according to the procedure described in Prep. No.# 25in U.S. patent application Ser. No. 11/277162, filed on Mar. 22, 2006entitled “PERFLUOROPOLYETHER URETHANE ADDITIVES HAVING (METH)ACRYLGROUPS AND HARD COATS” from HFPO—C(O)NHCH₂CH(OH)CH₂OH and CH₂═CHC(O)Cl.HFPO—C(O)NHCH₂CH(OH)CH₂OH was prepared according to Preparation No. 6 orparagraph [0066], of U.S. Patent Pub. No. 2005/0249956.

To a 250 ml 3 necked round bottom flask equipped with overhead stirrerwas charged 63.5 g (0.05 mol) of HFPO—C(O)NHCH₂CH(OH)CH₂OH, 9.56 g(0.946 mol) triethylamine and 100 g ethyl acetate. To the flask at roomtemperature was added 11.26 g (0.0945 mol) acryloyl chloride using apressure-equalizing dropping funnel over 12 min, with the reactiontemperature rising from 25 to a maximum of 40 degree C. The droppingfunnel was rinsed with 5 g additional ethyl acetate that was added tothe reaction that was then placed in a 40 degree C. bath and allowed toreact for 2 hours and 10 min additional time. The organic layer was thensuccessively washed with 65 g 2% aqueous sulfuric acid, 65 g 2% aqueoussodium bicarbonate, and 65 g water, dried over anhydrous magnesiumsulfate, filtered, treated with 16 mg methoxyhydroquinone (MEHQ), andconcentrated on a rotary evaporator at 45 degree C. to yield 62.8 g ofcrude product. Next 35 g of this material was chromatographed on 600 mlof silica gel (SX0143U-3, Grade 62, 60-200 mesh, EM Science) using 25:75ethyl acetate: heptane as an eluent. The first two fractions were 250 mlin volume, the remaining fractions were 125 ml in volume. Fractions 4-10were combined, 8 mg MEHQ was added to the fractions, which wereconcentrated on a rotary evaporator at 55 degree C. to provide productthat had a calculated wt-% fluorine of 58.5%

Preparation of FA-7,(ArO)CH₂CH(OAr)CH₂NHC(O)—HFPO—C(O)NHCH₂CH(OAr)CH₂OAr

(ArO)CH₂CH(OAr)CH₂NHC(O)—HFPO—C(O)NHCH₂CH(OAr)CH₂OAr was prepared fromCH₃OC(O)—HFPO—C(O)OCH₃ to(HO)CH₂CH(OH)CH₂NHC(O)—HFPO—C(O)NHCH₂CH(OH)CH₂OH by the reaction withNH₂CH₂CH(OH)CH₂OH, followed by reaction with CH₂═CHCO₂Cl, according tothe procedure described in Prep. No.# 26, of U.S. patent applicationSer. No. 11/277162, filed on Mar. 22, 2006, the disclosure of which isincorporated herein by reference in the preparation ofHFPO—C(O)NHCH₂CH(OAr)CH₂OAr from HFPO—C(O)OCH₃ whenCH₃O(O)C—HFPO—C(O)OCH₃ was used in replacement of HFPO—C(O)OCH₃ in thereaction with NH₂CH₂CH(OH)CH₂OH, followed by reaction with CH₂═CHCOCl.

Preparation of FA-8, Monofunctional Perfluoropolyether Methacrylate,HFPO—C(O)N(H)CH₂CH₂OC(O)C(CH₃)═CH₂

This compound is made by a procedure similar to that described in U.S.Publication No. 2004/0077775, entitled “Fluorochemical CompositionComprising a Fluorinated Polymer and Treatment of a Fibrous SubstrateTherewith,” filed on May 24, 2002, for Synthesis of(HFPO)k-methacrylate, substitutingF(CF(CF₃)CF₂O)_(x)CF(CF₃)C(O)NHCH₂CH₂OH with x=6.8, molecular weight1344, for the F(CF(CF₃)CF₂O)_(x)CF(CF₃)C(O)NHCH₂CH₂OH with x=10.5

Preparation of FA-9 MeFBSE-MDI-HEA (also referred to as C4MH)

C₄F₉SO₂N(CH₃)C₂H₄O—CONHC₆H₅CH₂C₆H₅NHCO—OC₂H₄OCOH═CH₂(MeFBSE-MDI-HEA) wasprepared according to the procedure described in U.S. Patent ApplicationPublication No. 2005/0143541, paragraph 0104.

C. Test Methods Method for Determining Contact Angle:

The coatings were rinsed for 1 minute by hand agitation in IPA beforebeing subjected to measurement of water and hexadecane contact angles.Measurements were made using as-received reagent-grade hexadecane “oil”(Aldrich) and deionized water filtered through a filtration systemobtained from Millipore Corporation (Billerica, Mass.), on a videocontact angle analyzer available as product number VCA-2500XE from ASTProducts (Billerica, Mass.). Reported values are the averages ofmeasurements on at least three drops measured on the right and the leftsides of the drops. Drop volumes were 5 μL for static measurements and1-3 μL for advancing and receding. For hexadecane, only advancing andreceding contact angles are reported because static and advancing valueswere found to be nearly equal.

Method for Determining Marker Repellency:

For this test one of the Sharpie Permanent Marker, Vis-à-vis PermanentOverhead Project Pen or King Size Permanent Marker (all commerciallyavailable from Sanford, USA) were used as the marker. First, the tip ofthe selected marker was cut with a razor blade to provide a wide flatmarking tip. Then, using the marker and an edge of a straight ruler as aguide, a straight line was drawn over the sample coatings applied over aPET substrate at an approximate speed of 15 cm per second. Theappearance of the straigt line drawn on the coatings was viewed and anumber was assigned to reflect the degree of repellency of the samplecoating towards markers. An assigned number of 1 indicates excellentrepellency while an assigned number of 5 indicates poor repellency.Depending on the type of marker used, the results are reported asSharpie test, Vis-à-vis test or King marker test. Method for DeterminingSolvent Resistance: For this test, a drop (about 1.25 cm in diameter) ofmethyl ethyl ketone (MEK) or other organic solvent was placed on asample coating applied over a PET substrate, and was allowed to dry atroom temperature. Afterwards, the sample coating was visually observedfor appearance and rated either as Haze (H), indicating poor solventrepellency or Clear (C), indicating good solvent repellency.Furthermore, using the above “method for marker test”, the sharpie testwas repeated on the spot where a drop of MEK or organic solventrepellency test was conducted, and a marker repellency number rangingfrom 1 to 5 was assigned.

Steel Wool Testing:

The abrasion resistance of the cured films was tested cross-web to thecoating direction by use of a mechanical device capable of oscillatingcheesecloth or steel wool fastened to a stylus (by means of a rubbergasket) across the film's surface. The stylus oscillated over a 10 cmwide sweep width at a rate of 3.5 wipes/second wherein a “wipe” isdefined as a single travel of 10 cm. The stylus had a flat, cylindricalgeometry with a diameter of 1.25 inch (3.2 cm). The device was equippedwith a platform on which weights were placed to increase the forceexerted by the stylus normal to the film's surface. The cheesecloth wasobtained from Summers Optical, EMS Packaging, a subdivision of EMSAcquisition Corp., Hatsfield, Pa. under the trade designation “Mil SpecCCC-c-440 Product # S12905”. The cheesecloth was folded into 12 layers.The steel wool was obtained from Rhodes-American, a division of HomaxProducts, Bellingham, Wash. under the trade designation“#0000-Super-Fine” and was used as received. A single sample was testedfor each example, with the weight in grams applied to the stylus and thenumber of wipes employed during testing reported. No visible scratchingis reported in the Tables as “NS”.

D. Preparation of hardcoat compositions and the resulting hardcoatlayers

Hardcoat compositions were prepared in weight % ratio as generallydescribed in the following tables. The coating on solar controlmultilayer film was at a dry thickness of about 4 microns using a wirewound rod. The coating were dried in a 110 degree Celsius oven for about1 to 2 minutes and then placed on a conveyor belt coupled to anultraviolet (UV) light curing device and UV cured using a Fusion 500watt H bulb (500 W) at 20 feet/minute. The coatings were then analyzedusing the above described test methods.

1. Urethane Containing HFPO multiacrylates as Additive in ATO HardcoatCompositions

1˜2% D-1173 (10% solution in MEK) was added to the 30% ATO-1nano-particle hardcoat dispersion, diluted with MEK.Fluoro-acrylate-additives, FA-1, FA-2, FA-3 and FA-4 were prepared asdiscussed above, are diluted with MEK, EtOAc or MEK/mixed solvents to30% solution, than added to ATO solution in different ratios. The 30%solution was coated on solar control multilayer films with No. #10 wirerod. The coated films were dried in 110° C. oven for ˜2 minutes, thenUV-cured under N₂ with H-bulb at 20 feet/minutes. The detailed coatingformulations and coating quality were recorded in Table I. Control-1 ispure ATO-1 formulation without any fluoro-acrylate-additive (0% FA).Control-2 is the formulation of ATO-2 with 0.06% FA-1 additive, and theformulation was coated using an extrusion die coating process and curedusing Fusion H and D bulbs (at 60% power) at 50 feet per minute toobtain a dry coating of approximately 2.6 microns thick. Following thehardcoat coating process, a pressure sensitive adhesive (PSA) coatingwas applied to the surface opposite the hardcoat surface and a siliconerelease liner was laminated thereto. The PSA coating was applied atapproximately 0.8 g/ft² dry coating weight.

TABLE I ATO Hardcoat Formulation with Perfluoropolyether Additive Exp.No# ATO FA FA % Coating Quality Control-1 ATO-1 None 0 Good Control-2ATO-2 FA-1 0.06 Good 1 ATO-1 FA-1 0.1 Good 2 ATO-1 FA-1 0.25 Good 3ATO-1 FA-1 0.5 Good 4 ATO-1 FA-1 1.0 Good 5 ATO-1 FA-1 2.0 Good 6 ATO-1FA-2 0.5 Good 7 ATO-1 FA-3 0.5 Good 8 ATO-1 FA-4 0.5 Good

The marker repellent and contact angle were measured as discussed aboveand the results from the formulations of Table I are summarized in TableII.

TABLE II Marker Repellent and Contact Angle Data with PerfluoropolyetherAdditive King Vis- H₂O Contact Oil Contact Exp. Sharpie Size à-vis AngleAdv/ Angle Adv/ No# Test Test Test Rec/Static (°) Rec/Static (°)Control-1 5 5 5 79/45/71 10/5/13 Control-2 3 5 3 110/53/99 55/43/54 1 11 1 103/75/100 60/50/57 2 1 1 1 106/82/102 68/60/63 3 1 1 1 110/88/10972/64/67 4 1 1 1 124/99/120 74/63/68 5 1 1 1 115/88/111 70/63/66 6 1 1 1116/88/110 69/61/67 7 1 1 1 115/90/107 68/62/66 8 2 1 2 100/73/9455/45/52

From the above results it can be seen that, 0.25˜1% of FA-1 providesdesirable results with respect to repellency for easy cleaningperformance

The solvent resistance and corresponding sharpie marker tests wereperformed as discussed above and the results are recorded in Table III.

TABLE III Solvent Resistance with Perfluoropolyether Additive on PETExp, No# IPA Toluene MIBK Acetone EtOAc MEK DMF 1 C/1 C/1 C/1 C/1 C/1C/1 C/1 2 C/1 C/1 C/1 C/1 C/1 C/1 C/1 3 C/1 C/1 C/1 C/1 C/1 C/1 C/1 4C/1 C/1 C/1 C/1 C/1 C/1 C/1 5 C/1 C/1 C/1 C/1 C/1 C/1 C/1 6 C/1 C/1 C/1C/1 C/1 C/1 C/1 7 C/1 C/1 C/1 C/1 C/1 C/1 C/1 8 C/1 C/1 C/1 C/1 C/1 C/1C/1 Connol-1 C/5 C/5 C/5 C/5 C/5 C/5 C/5 Control-2 C/3 C/3 C/3 C/3 C/3C/3 C/3

All of the hardcoats showed excellent solvent resistance, and noappearance change was observed with selected solvents, which indicatedthat the coating was tolerant to cleaning with solvent-born cleaningformulations. All the sharpie marker repellency also remained after thesolvent test.

These improvements in solvent resistance, marker repellency, andmechanical durability that are exhibited by at least some embodiments ofthe invention may be due at least art by the degree of crosslinkingdegree in the hardcoat layers that are formed from compositions of theinvention. Generally, such a degree of crosslinking is unattainable fromnon-UV cured polymerization processes. It has also been suggested thatboth high water/oil contact angles and good solvent resistance may helpin achieving high marker repellency characteristics.

The durability testing was performed as discussed above and the resultsare shown in Table IV below.

TABLE IV Steel Wool Test Results and Refractive Index Measurement*Before steel After steel wool Exp. wool Ink Ink Coating H₂O ContactAngle Oil Contact Angle No# repellence repellence AppearanceAdv/Rec/Static Adv/Rec/Static Control-2 Y No NS 66/15/65 27/13/25 1a** YY NS 116/98/110 70/63/69 2 Y Y NS 111/78/98 67/55/64 3 Y Y NS 118/80/11249/34/46 3a** Y Y NS 108/97/105 50/44/47 4 Y Y NS 115/82/110 69/52/65 5Y Y NS 119/86/111 68/46/62 *Steel wool test by 1.25 inch stylus, 500 gweight and 300 rubs; **Coated with No. 30 wire rod.

2. Urethane Containing HFPO multiacrylates as Additive in ATO HardcoatCompositions

Contact angles of water and hexadecane were tested for hardcoatcompositions that included fluoro-acrylate-non-urethane additives. Theparticular formulations and results of testign can be seen in Tables V,VI, VII and VIII below.

Generally, the additive (FA-5, FA-6, FA-7, and FA-8) was diluted in MEKto give a 10wt-% solution. The ATO was diluted with Carbitol to make a30% solution that included 1wt-% D-1173 (photo initiator). The additivesolution and the ATO solution were then combined in the ratios given inthe respective Tables below. Contact angles and marker repellencytesting was then carried out and the results are presented below.

TABLE V (HFPO)x—CONHC₃H₆NHCH₃/TMPTA additive (FA-5) to ATO hardcoat:Formulation Exp. (Ratio by Coating H₂O HD Marker Test No# weight)Quality Adv Rec Static Adv Rec Static King Vis a Vis Sharpie 9 ATO/FA-5Good 114 95 107 64 57 63 1 1 1 (99.75/0.25) 113 88 106 72 59 63 110 87106 70 60 69 Average 112.3 90.0 106.3 68.7 58.7 65.0 10 ATO/FA-5 OK 11493 105 73 53 70 1 1 1 (99.5/0.5) (small 116 93 108 72 52 70 Averagebeads) 115 93 106.5 72.5 52.5 70 11 ATO/FA-5 some 113 88 109 73 64 73 11 1 (99.0/1.0) dewet 114 94 110 73 63 73 112 93 108 Average 113.0 91.7109.0 73.0 63.5 73.0

TABLE VI (HFPO)x—CONHCH₂CH(OAr)CH₂OAr (FA-6) Additive to ATO hardcoat:Formulation Exp. (Ratio by Coating H₂O HD Marker Test No# weight)Quality Adv Rec Static Adv Rec Static King Vis a Vis Sharpie 12 ATO/FA-6OK 119 106 110 73 67 72 1 1 1 (99.75/0.25) 115 105 110 69 65 72 117 104112 73 64 72 Average 117.0 105.0 110.7 71.7 65.3 72.0 13 ATO/FA-6 OK 119102 111 72 63 71 1 1 1 (99.5/0.5) 118 103 113 72 63 71 Average 119 102.5112 72 63 71 14 ATO/FA-6 Good 121 102 114 72 65 71 1 2 1 (99.0/1.0) 117100 112 72 65 72 120 102 113 Average 119.3 101.3 113.0 72.0 65.0 71.5

TABLE VII (ArO)CH₂CH(OAr)CH₂NHC(O)—HFPO—C(O)NHCH₂CH(OAr)CH₂OAr (FA-7,10% in MEK) Additive to ATO hardcoat: Exp. Coating H₂O HD Marker TestNo# Formulation Quality Adv Rec Static Adv Rec Static King Vis a VisSharpie 15 ATO/FA-7 Good 113 95 107 68 57 68 1 2 1 (99.75/0.25) 112 94106 67 55 69 Average 112.5 94.5 106.5 67.5 56 68.5 16 ATO/FA-7 Good 11298 108 70 55 67 1 2 1 (99.5/0.5) 112 97 109 70 56 69 Average 112 97.5108.5 70 55.5 68 17 ATO/FA-7 Good 114 96 107 71 60 69 1 1 1 (99.0/1.0)114 97 107 71 60 69 Average 114 96.5 107 71 60 69

TABLE VIII (HFPO)x—CONHC₂H₄OC(O)CMe═CH₂ (FA-8) Additive to ATO hardcoat:Exp. Formulation Coating H₂O HD Marker Test No# (Ratio by weight)Quality Adv Rec Static Adv Rec Static King Vis a Vis Sharpie 18 ATO/FA-8some 99 77 95 46 33 43 2 2 2 (99.75/0.25) dewet 99 77 95 48 35 45Average 99 77 95 47 34 44 19 ATO/FA-8/ OK 102 80 99 65 45 57 1 2 2MeFBSEA 100 78 97 65 44 58 (99.75/0.25/5) 101 79 98 65 44.5 57.5 20ATO/FA-8 Good 102 83 95 55 43 50 1 2 1 (99.5/0.5) 103 81 93 55 42 51Average 103 82 94 55 42.5 50.5 21 ATO/FA-8 Good 110 92 103 70 57 70 1 11 (99.0/1.0) 111 92 105 69 58 68 Average 111 92 104 70 57.5 69

As seen in Tables V, VI, VII and VIII, all of thefluoro-acrylate-non-urethane additives that were tested producedhardcoat layers with desirable properties, such as solvent resistance toacetone, toluene, IPA, MIBK, EtOAc and DMF, and good durability to SteelWood abrasive test.

3. MeFBSE-MDI-HEA (FA-9) as Additive for UV Curable ATO Hardcoat:

An ATO-1 nano-particle hardcoat was combined with 1% D-1173photo-initiator (10% solution in MEK), and then diluted with MEK to a20% solution. Fluoro-acrylate-additives were added along with ahydrosilylation catalyst, platinum-divinyltetamethydisiloxane complex(CAS# 68478-92-2), at 0.015% by weight, and then diluted with heptane toa 10% solution. The ˜20% solution of ATO/Additive was formulated indifferent ratio by weight (based on Table V below), and coated on PETfilm with a No. #10 wire rod. The coated films were dried in 110° C.oven for ˜5 minutes, then UV-cured under N₂ with H-bulb (100% power) at20 feet per minute. The detailed coating formulations, coating qualitywere recorded in Table IX. The marker repellent, contact angle data andsolvent results are summarized in Table X and XI.

TABLE IX ATO Hardcoat Formulation with MeFBSE-MDI-HEA (FA-9) AdditiveExp. ATO-1 FA-9 No# (30% solution) (30% solution) Coating Quality 2299.0% 1.0% Good 23 98.0% 2.0% Good 24 95.0% 5.0% Good

TABLE X Marker Repellent and Contact Angle Data with PerfluoropolyetherAdditive* King Vis- Exp. Sharpie Size à-vis H₂O Contact Angle OilContact Angle No# Test Test Test Adv/Rec/Static (°) Adv/Rec/Static (°)22 5 5 5 Not measured Not measured 23 1 1 1 118/100/107 75/69/72 24 1 11 118/87/115 70/55/66

TABLE XI Solvent Resistance with Perfluoropolyether Additive on PET Exp.No# IPA Toluene MIBK Acetone EtOAc MEK DMF 22 C/1 C/1 C/1 C/1 C/1 C/1C/1 23 C/1 C/1 C/1 C/1 C/1 C/1 C/1

4. Properties of Solar Control Article

A multilayer film containing about 446 layers was made on a sequentialflat-film making line via a coextrusion process. This multilayer polymerfilm was made from coPEN and PETG (available from Eastman Chemicals).The coPEN was polymerized with 90% PEN and 10% PET starting monomers. Afeedblock method (such as that described by U.S. Pat. No. 3,801,429) wasused to generate about 223 optical layers with an approximately linearlayer thickness gradient from layer to layer through the extrudate.

The coPEN was delivered to the feedblock by an extruder at a rate ofabout 132 lb/hr and the PETG at about 160 lb/hr. A portion of the PETGis used as protective boundary layers (PBL's) on each side of theextrudate with about 32 lb/hr flow total. The material stream thenpassed though an asymmetric two times multiplier with a multiplierdesign ratio of about 1.25. Multiplier concepts and function aredescribed in U.S. Pat. Nos. 5,094,788 and 5,094,793. The multiplierratio is defined as the average layer thickness of layers produced inthe major conduit divided by the average layer thickness of layers inthe minor conduit. This multiplier ratio was chosen so as to provide asmall overlap of the two reflectance bands created by the two sets of223 layers. Each set of 223 layers has the approximate layer thicknessprofile created by the feedblock, with overall thickness scale factorsdetermined by the multiplier and film extrusion rates. After themultiplier, skin layers were added at about 72 lbs/hour (total) that wasfed from a third extruder. Then the material stream passed through afilm die and onto a water cooled casting wheel.

The PETG melt process equipment was maintained at about 500° F., thecoPEN (both optics and skin layers) melt process equipment wasmaintained at about 525° F., and the feedblock, multiplier, skin-layermeltstream, and die were maintained at about 525° F.

The feedblock used to make the film for this example was designed togive a linear layer thickness distribution with a 1.3:1 ratio ofthickest to thinnest layers under isothermal conditions. Errors in thislayer profile are corrected with the axial rod heater profile, asdescribed in U.S. Pat. No. 6,827,886, which is incorporated by referenceherein. The casting wheel speed was adjusted for precise control offinal film thickness, and therefore, final bandedge position.

The inlet water temperature on the casting wheel was about 7° Celsius. Ahigh voltage pinning system was used to pin the extrudate to the castingwheel. The pinning wire was about 0.17 mm thick and a voltage of about6.5 kV was applied. The pinning wire was positioned manually by anoperator about 3 to 5 mm from the web at the point of contact to thecasting wheel to obtain a smooth appearance to the cast web. The castweb was continuously oriented by conventional sequential length orienter(LO) and tenter equipment. The web was length oriented to a draw ratioof about 3.8 at about 270° F. The film was preheated to about 255° F. inabout 15 seconds in the tenter and drawn in the transverse direction toa draw ratio of about 3.5 at 270° F. The film was heat set in the tenteroven at a temperature of about 460° F. for about 30 seconds. Thefinished film had a final thickness of about 0.0035 inches.

The multilayer film, as prepared above was then coated with the“Control-2” formulation referred to in Table I above, dried, and curedas described above. The optical transmission and reflection spectra ofthe article were measured using a Lambda 19 spectrophotometer (PerkinElmer, Boston Mass.). The spectra were then imported into Optics 4 andWindows 5.2 programs available from Lawrence Berkeley NationalLaboratories for analyzing thermal and optical properties of glazingsystems. The programs can be downloaded fromhttp://windows.lbl.gov/software/.

Solar heat gain coefficient (“SHGC”) is the fraction of incident solarradiation admitted through a window, both directly transmitted andabsorbed and subsequently released inward. SHGC is expressed as a numberbetween 0 and 1. The lower a window's SHGC, the less solar heat ittransmits. Table XII shows the solar performance of the article.

TABLE XII Solar Performance of Article with Hardcoat from “Control-2”Formulation Solar Heat Total Visible Light Gain Co- Total Solar SolarTotal Solar Transmission efficient Haze Transmission ReflectionAbsorption (%) (SHGC) (%) (%) (%) (%) 71 0.51 1 41 24 35

The present invention should not be considered limited to the particularexamples described above, but rather should be understood to cover allaspects of the invention as fairly set out in the attached claims.Various modifications, equivalent processes, as well as numerousstructures to which the present invention may be applicable will bereadily apparent to those of skill in the art to which the presentinvention is directed upon review of the instant specification.

1. An article comprising: an infrared light reflecting multilayer filmhaving alternating layers of a first polymer type and a second polymertype; and a hardcoat layer disposed on the multilayer film, wherein saidhardcoat layer comprises infrared light absorbing nanoparticlesdispersed therein and wherein the hardcoat layer has a static contactangle of water that is greater than 70 degrees, and a static contactangle of hexadecane that is greater than 50 degrees.
 2. The articleaccording to claim 1 further comprising a pressure sensitive adhesivelayer disposed on the multilayer film, the pressure sensitive adhesivelayer being disposed on the opposing surface of the multilayer film asthe hardcoat layer.
 3. The article according to claim 2 furthercomprising a release liner disposed on the pressure sensitive adhesivelayer, the pressure sensitive adhesive layer disposed between therelease liner and the multilayer film layer.
 4. The article according toclaim 1 further comprising a tear resistant multilayer film havingalternating layers of a stiff polyester or copolyester and a ductilesebacic acid based co-polyester.
 5. The article according to claim 1,wherein said hardcoat layer has a static contact angle of water that isgreater than 90 degrees.
 6. The article according to claim 1, whereinsaid hardcoat layer has a static contact angle of water that is greaterthan 100 degrees.
 7. The article according to claim 1, wherein saidhardcoat layer has a static contact angle of hexadecane that is greaterthan 60 degrees.
 8. The article according to claim 1, wherein saidhardcoat layer comprises the reaction product of a mixture comprising:at least one curable, crosslinkable compound comprising afluoro-containing moiety; at least one curable, crosslinkablenon-fluorinated compound; an infrared absorbing material; and apolymerization initiator.
 9. The article according to claim 8, whereinthe infrared absorbing material is metal oxide nanoparticles.
 10. Thearticle according to claim 9, wherein the metal oxide nanoparticles areantimony tin oxide, indium tin oxide, or a combination thereof.
 11. Anarticle comprising: an infrared light reflecting multilayer film havingalternating layers of a first polymer type and a second polymer type;and a hardcoat layer disposed on the multilayer film, wherein saidhardcoat layer comprises the reaction product of a mixture comprising:at least one curable, crosslinkable fluoro-acrylate-containing compound;at least one curable, crosslinkable non-fluorinated compound; infraredlight absorbing nanoparticles; and a polymerization initiator.
 12. Thearticle according to claim 11, wherein the fluoro-moiety is afluoroalkyl moiety or a perfluoropolyether moiety.
 13. The articleaccording to claim 11, wherein the fluoro-moiety is a)F(R_(fc)O)_(x)C_(d)F_(2d)— or —C_(d)F_(2d)O(R_(fc)O)_(x)C_(d)F_(2d)wherein each R_(fc) independently represents a fluorinated alkylenegroup having from 1 to 6 carbon atoms, each x independently representsan integer greater than or equal to 2, C_(d)F_(2d) can be linear orbranched, and wherein d is an integer from 1 to 8; or b) C_(d)F_(2d+1),wherein d is 1 to 8; or. c) CF₃CF₂CF₂CHFCF₂—; CF₃CHFO(CF₂)₃—;(CF₃)₂NCF₂CF₂—; CF₃CF₂CF₂OCF₂CF₂—; CF₃CF₂CF₂OCHCF₂—; n-C₃F₇OCF(CF₃)—;H(CF₂CF₂)₃—; or n-C₃F₇OCF(CF₃)CF₂OCF₂—.
 14. The article according toclaim 11, wherein the fluoro-acrylate-containing compound is:(R_(f)QXC(O)NH))_(m)—R_(i)—(NHC(O)OQ(A)_(a))_(n)   (Formula 1) whereinR_(i) is a residue of a multi-isocyanate; X is O, S or NR, where R is Hor lower alkyl of 1to 4 carbon atoms; R_(f) is a monovalentperfluoropolyether moiety composed of groups comprising the formula ofF(R_(fc)O)_(x)C_(d)F_(2d)— wherein each R_(fc) independently representsa fluorinated alkylene group having from 1 to 6 carbon atoms; xindependently represents an integer greater than or equal to 2;C_(d)F_(2d) can be linear or branched, and d is an integer from 1 to 8;Q is independently a connecting group with a valence of at least 2; A isa (meth)acryl functional group —XC(O)C(R²)═CH₂, where R² is a loweralkyl of 1 to 4 carbon atoms or H or F, and X is as defined above; m isat least 1; n is at least 1; and a is 1 to 6, with the proviso that m+nis 2 to 10, and in which each unit referred to by the subscripts m and nis attached to an R_(i) unit.
 15. The article according to claim 14,wherein the fluoro-acrylate-containing compound is


16. The article according to claim 11, wherein thefluoro-acrylate-containing compound isR_(f2)-[Q-(XC(O)NHQOC(O)C(R²)═CH₂)_(a)]_(g)   (Formula 2) wherein R_(f2)is either a monovalent perfluoropolyether moiety composed of groupscomprising the formula F(R_(fc)O)_(x)C_(d)F_(2d)— or a divalentperfluoropolyether moiety composed of groups comprising the formula—C_(d)F_(2d)O(R_(fc)O)_(x)C_(d)F_(2d)—, wherein each R_(fC)independently represents a fluorinated alkylene group having from 1 to 6carbon atoms; x independently represents an integer greater than orequal to 2; C_(d)F_(2d) can be linear or branched, and d is an integerfrom 1 to 8; Q is independently a connecting group havinga valence of atleast 2; X is O, S or NR, where R is H or lower alkyl of 1 to 4 carbonatoms; R² is a lower alkyl of 1 to 4 carbon atoms or H or F; a is from 1to 6; and g is 1 or
 2. 17. The article according to claim 16, whereinthe fluoro-acrylate-containing compound isHFPO—C(O)NHC₂H₄OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂,HFPO—C(O)NHC(C₂H₅)(CH₂OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂)₂,HFPO—[C(O)NHC₂H₄OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂]₂,HFPO—[C(O)NHC(C₂H₅)(CH₂OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂)₂]₂,HFPO—C(O)NHCH₂CH[OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂]CH₂OC(O)NHC₂H₄OC(O)C(CH₃)═CH,HFPO—C(O)NHC(C₂H₅)(CH₂OC(O)NHC₂H₄OC(O)C(CH₃)=CH₂)₂, CH₂═C(CH₃)C(O)OC₂H₄NHC(O)OC₂H₄NHC(O)—HFPO—C(O)NHC₂H₄OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂,HFPO—C(O)NH(C₂H₄N(C(O)NHC₂H₄OC(O)C(CH₃)═CH₂)₄C₂H₄NHC(O)—HFPO, or acombination thereof.
 18. The article according to claim 11, wherein thefluoro-acrylate-containing compound is

wherein R_(i) is a residue of a multi-isocyanate; X is O, S or NR, whereR is H or lower alkyl of 1 to 4 carbon atoms; R_(f) is a monovalentperfluoropolyether moiety composed of groups comprising the formulaF(R_(fc)O)_(x)C_(d)F_(2d)—, wherein each R_(fc) independently representsa fluorinated alkylene group having from 1 to 6 carbon atoms; xindependently represents an integer greater than or equal to 2; and d isan integer from 1 to 8; Q is independently a connecting group of valencyat least 2; A is a (meth)acryl functional group —XC(O)C(R²)═CH₂, whereR² is a lower alkyl of 1 to 4 carbon atoms or H or F; G is alkyl, aryl,alkaryl, aralkyl group, substituted alkyl/aryl group; m is at least 1; nis at least 1; o is at least 1; and a is 2 to
 6. 19. The articleaccording to claim 11, wherein the fluoro-acrylate-containing compoundis

wherein R_(i) is a residue of a multi-isocyanate; X is O, S or NR, whereR is H or lower alkyl of 1 to 4 carbon atoms; R^(f) is a monovalentperfluoropolyether moiety composed of groups comprising the formulaF(R_(fc)O)_(x)C_(d)F_(2d)—, wherein each R_(fc) independently representsa fluorinated alkylene group having from 1 to 6 carbon atoms; xindependently represents an integer greater than or equal to 2;C_(d)F_(2d) can be linear or branched, and d is an integer from 1 to 8;Q is independently a connecting group of valency at least 2; A is a(meth)acryl functional group —XC(O)C(R²)═CH₂, where R² is a lower alkylof 1 to 4 carbon atoms or H or F; m is at least 1; n is at least 1; a is1 to 6; and D is a divalent or q-valent isocyanate reactive residue. 20.The article according to claim 11, wherein thefluoro-acrylate-containing compound is:(R_(f2))—[(W)—(R_(A))_(a)]_(g)   (Formula 5) wherein R_(f2) is amonovalent perfluoropolyether moiety composed of groups comprising theformula F(R_(fc)O)_(x)C_(d)F_(2d)—, or divalent perfluoropolyether groupcomposed of groups comprising the formula—C_(d)F_(2d)O(R_(fc)O)_(x)C_(d)F_(2d)—, wherein each R_(fc)independently represents a fluorinated alkylene group having from 1 to 6carbon atoms; x independently represents an integer greater than orequal to 2; C_(d)F_(2d) can be linear or branched, and d is an integerfrom 1 to 8; W is a linking group; and R_(A) is a free-radicallyreactive group; a is 1 to 6, and g is 1 or
 2. 21. The article accordingto claim 20, wherein the fluoro-acrylate-containing compound isHFPO—[C(O)NHCH₂CH₂OC(O)CH═CH₂]_(1˜2),HFPO—[C(O)NHCH₂CH₂OCH₂CH₂OCH₂CH₂OC(O)CH═CH₂]_(1˜2),HFPO—[C(O)NH—(CH₂)₆OC(O)CH═CH]_(1˜2),HFPO—[C(O)NHC(CH₂OC(O)CH═CH₂)₃]_(1˜2),HFPO—[C(O)N(CH₂CH₂OC(O)CH═CH₂)₂]_(1˜2),HFPO—[C(O)NHCH₂CH₂N(C(O)CH═CH₂)CH₂OC(O)CH═CH₂]_(1˜2),HFPO—[C(O)NHC(CH₂OC(O)CH═CH₂)₂H]_(1˜2),HFPO—[C(O)NHC(CH₂OC(O)CH═CH₂)₂CH₃]_(1˜2),HFPO—[C(O)NHC(CH₂OC(O)CH═CH₂)₂CH₂CH₃]_(1˜2),HFPO—[C(O)NHCH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂]_(1˜2),HFPO—[C(O)NHCH₂CH₂CH₂N(CH₂CH₂OC(O)CH═CH₂)₂]_(1˜2),HFPO—[C(O)OCH₂C(CH₂OC(O)CH═CH₂)₃]_(1˜2),CH₂═CHC(O)OCH₂CH(OC(O)HFPO)CH₂OCH₂CH(OH)CH₂OCH₂CH(OC(O)HFPO)CH₂OCOCH═CH₂, HFPO—CH₂O—CH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂;HFPO—[CH₂O—CH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂]₂;HFPO—C(O)N(H)CH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂,(ArO)CH₂CH(OAr)CH₂NHC(O)—HFPO—C(O)NHCH₂CH(OAr)CH₂OAr,HFPO—C(O)N(H)CH₂CH₂OC(O)C(CH₃)═CH₂,CH₂═CHC(O)OCH₂CF₂O(CF₂CF₂O)_(x1)(CF₂O)_(x2n)CH₂OC(O)CH═CH₂,HFPO—[C(O)NHCH₂CH₂OC(O)CH₂SH]_(1˜2, HFPO—[C(O)NHCH) ₂CH═CH₂]_(1˜2),HFPO—[C(O)NHCH₂CH₂OCH═CH₂]_(1˜2), HFPO—CH₂OC(O)CH═CH₂,HFPO—CH₂CH₂OC(O)CH═CH₂, HFPO—CH₂CH₂OC(O)C(CH₃)═CH₂,HFPO—CH₂CH₂OCH₂CH₂OC(O)CH═CH₂, or combinations thereof.
 22. The articleaccording to claim 11, wherein the fluoro-acrylate-containing compoundis:R_(f3)-J-OC(O)NH—K—HNC(O)O—(C_(b)H_(2b))CH_((3−v))((C_(y)H_(2y))OC(O)C(R²)═CH₂)_(v)  (Formula 6) wherein, R_(f3) is C_(d)F_(2d+1), wherein d is 1 to 8, orCF₃CF₂CF₂CHFCF₂—, CF₃CHFO(CF₂)₃—, (CF₃)₂NCF₂CF₂—, CF₃CF₂CF₂OCF₂CF₂—,CF₃CF₂CF₂OCHF₂—, n-C₃F₇OCF(CF₃)—, H(CF₂CF₂)₃—, orn-C₃F₇OCF(CF₃)CF₂OCF₂—;

wherein R is H or an alkyl group of 1 to 4 carbon atoms; h is 2 to 8; jis 1 to 5; y is 0 to 6; K is the residue of a diisocyanate with anunbranched symmetric alkylene group, arylene group, or aralkylene group;b is 1 to 30; y is 1 to 5; v is 1 to 3; and R² is H, CH₃, or F.
 23. Thearticle according to claim 22, wherein the fluoro-acrylate-containingcompound is C₄F₉SO₂N(CH₃)C₂H₄O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(MeFBSE-MDI-HEA), C₄F₉SO₂N(CH₃)C₂H₄O—C(O)NH(CH₂)₆NHC(O)—OC₂H₄OC(O)Me=CH₂(MeFBSE-HDI-HEMA),C₄F₉SO₂N(CH₃)C₂H₄O—C(O)NH(CH₂)₆NHC(O)—OC₄H₈OC(O)CH═CH₂ (MeFBSE-HDI-BA),C₄F₉SO₂N(CH₃)C₂H₄)—C(O)NH(CH₂)₆NHC(O)—OC₁₂H₂₄OC(O)CH═CH₂(MeFBS-HDI-DDA), CF₃CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(CF₃CH₂OH-MDI-HEA), C₄F₉CH₂CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₄F₉CH₂CH₂OH-MDI-HEA),C₆F₁₃CH₂CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₆F₁₃CH₂CH₂OH—MDI—HEA),C₃F₇CHFCF₂CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₃F₇CHFCF₂CH₂OH-MID-HEA),CF₃CHFO(CF₂)₃CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(CF₃CHFO(CF₂)₃CH₂O-MDI—HEA),C₃F₇OCHFCF₂CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₃F₇OCHFCF₂CH₂OH-MDI—HEA),C₃F₇OCF(CF₃)CH₂O—C(O)NHC₆H₅CH₂C₆H₅NHC(O)—OC₂H₄OC(O)CH═CH₂(C₃F₇OCF(CF₃)CH₂OH-MDI—HEA),C₄F₉SO₂NMeC₂H₄O—C(O)NHC₆H₄CH₂C₆H₄NHC(O)—OCH₂C(CH₂OC(O)CH═CH₂)₃(MeFBSE-MDI-(SR-444C)), or combinations thereof.
 24. The articleaccording to claim 11 further comprising a pressure sensitive adhesivelayer disposed on the multilayer film, the pressure sensitive adhesivelayer being disposed on the opposing surface of the multilayer film asthe hardcoat layer.
 25. The article according to claim 24 furthercomprising a release liner disposed on the pressure sensitive adhesivelayer, the pressure sensitive adhesive layer disposed between therelease liner and the multilayer film layer.
 26. The article accordingto claim 11 further comprising a tear resistant polymeric film.
 27. Alight control article for blocking infrared light from an infrared lightsource comprising: an infrared light reflecting multilayer film havingalternating layers of a first polymer type and a second polymer type; ahardcoat layer disposed on the multilayer film, wherein said hardcoatlayer comprises the reaction product of a mixture comprising: a curable,crosslinkable fluoro-acrylate-containing compound; a curable,crosslinkable non-fluorinated organic compound; infrared light absorbingnanoparticles; and a polymerization initiator; and a substrate disposedadjacent the infrared light reflecting multilayer film.
 28. The lightcontrol article according to claim 27 further comprising a pressuresensitive adhesive layer disposed between the infrared light reflectingmultilayer film and the glass substrate.
 29. The light control articleaccording to claim 27 further comprising a tear resistant polymericfilm.
 30. The light control article according to claim 27, wherein thehardcoat layer has a thickness in a range from 1 to 20 micrometers.